Novel herbicides

ABSTRACT

Compounds of formula (I) wherein the substituents are as defined in claim  1 , are suitable for use as herbicides.

The present invention relates to novel, herbicidally active cyclopentanedione compounds, and derivatives thereof, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting undesired plant growth.

Cyclopentanedione compounds having herbicidal action are described, for example, in WO 01/74770 and WO 96/03366.

Novel cyclopentanedione compounds, and derivatives thereof, having herbicidal and growth-inhibiting properties have now been found.

The present invention accordingly relates to compounds of formula I

wherein G is hydrogen or an alkali metal, alkaline earth metal, sulfonium, ammonium or a latentiating group, R¹ is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, ethynyl, halogen, C₁-C₂alkoxy or C₁-C₂haloalkoxy, R², R³ and R⁴ are independently of each other hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, ethynyl, halogen, C₁-C₂alkoxy or C₁-C₂ haloalkoxy, R⁵ and R¹² are independently of each other hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkyoxy, C₁-C₃alkylthio, halogen or C₁-C₆alkoxycarbonyl, or R⁵ and R¹² join together to form a 3-7 membered carbocyclic ring, optionally containing an oxygen or sulfur atom, and R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are independently of each other hydrogen or a substituent, or R⁷ and R⁸, or R⁹ and R¹⁰, together with the carbon atoms to which they are attached form a keto, an optionally substituted alkenyl or optionally substituted imino unit, or any two of R⁷, R⁸, R⁹ and R¹⁰ together form a 3-8 membered carbocyclic ring optionally containing a heteroatom selected from O, S or N and optionally substituted, or R⁷ and R¹⁰ together form a bond.

In the substituent definitions of the compounds of the formula I, each alkyl moiety either alone or as part of a larger group (such as alkoxy, alkylthio, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl) is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or neopentyl. The alkyl groups are suitably C₁-C₆ alkyl groups, but are preferably C₁-C₄ alkyl or C₁-C₃ alkyl groups, and, more preferably, C₁-C₂alkyl groups.

When present, the optional substituents on an alkyl moiety (alone or as part of a larger group such as alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl) include one or more of halogen, nitro, cyano, C₃₋₇ cycloalkyl (itself optionally substituted with C₁₋₆ alkyl or halogen), C₅₋₇ cycloalkenyl (itself optionally substituted with C₁₋₆ alkyl or halogen), hydroxy, C₁₋₁₀ alkoxy, C₁₋₁₀ alkoxy(C₁₋₁₀)alkoxy, tri(C₁₋₄)alkylsilyl(C₁₋₆)alkoxy, C₁₋₆ alkoxycarbonyl(C₁₋₁₀)alkoxy, C₁₋₁₀ haloalkoxy, aryl(C₁₋₄)-alkoxy (where the aryl group is optionally substituted), C₃₋₇ cycloalkyloxy (where the cycloalkyl group is optionally substituted with C₁₋₆ alkyl or halogen), C₃₋₁₀ alkenyloxy, C₃₋₁₀ alkynyloxy, mercapto, C₁₋₁₀ alkylthio, C₁₋₁₀ haloalkylthio, aryl(C₁₋₄)alkylthio (where the aryl group is optionally substituted), C₃₋₇ cycloalkylthio (where the cycloalkyl group is optionally substituted with C₁₋₆ alkyl or halogen), tri(C₁₋₄)alkylsilyl(C₁₋₆)alkylthio, arylthio (where the aryl group is optionally substituted), C₁₋₆ alkylsulfonyl, C₁₋₆ haloalkylsulfonyl, C₁₋₆ alkylsulfinyl, C₁₋₆ haloalkylsulfinyl, arylsulfonyl (where the aryl group may be optionally substituted), tri(C₁₋₄) alkylsilyl, aryldi(C₁₋₄)alkylsilyl, triarylsilyl, aryl(C₁₋₄)alkylthio(C₁₋₄)alkyl, aryloxy(C₁₋₄)alkyl, formyl, C₁₋₁₀ alkylcarbonyl, HO₂C, C₁₋₁₀ alkoxycarbonyl, aminocarbonyl, C₁₋₆ alkylaminocarbonyl, di(C₁₋₆ alkyl)aminocarbonyl, N—(C₁₋₃ alkyl)-N—(C₁₋₄ alkoxy)aminocarbonyl, C₁₋₆ alkylcarbonyloxy, arylcarbonyloxy (where the aryl group is optionally substituted), di(C₁₋₆)alkylaminocarbonyloxy, C₁₋₆alkyliminooxy, C₃₋₆alkenyloxyimino, aryloxyimino, aryl (itself optionally substituted), heteroaryl (itself optionally substituted), heterocyclyl (itself optionally substituted with C₁₋₆ alkyl or halogen), aryloxy (where the aryl group is optionally substituted), heteroaryloxy, (where the heteroaryl group is optionally substituted), heterocyclyloxy (where the heterocyclyl group is optionally substituted with C₁₋₆ alkyl or halogen), amino, C₁₋₆ alkylamino, di(C₁₋₆)alkylamino, C₁₋₆ alkylcarbonylamino, N—(C₁₋₆)alkylcarbonyl-N—(C₁₋₆)alkylamino, C₂₋₆ alkenylcarbonyl, C₂₋₆ alkynylcarbonyl, C₃₋₆ alkenyloxycarbonyl, C₃₋₆ alkynyloxycarbonyl, aryloxycarbonyl (where the aryl group is optionally substituted) and arylcarbonyl (where the aryl group is optionally substituted).

Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or (Z)-configuration. Examples are vinyl, allyl and propargyl. Alkenyl and alkynyl moieties can contain one or more double and/or triple bonds in any combination. It is understood, that allenyl and alkylinylalkenyl are included in these terms. It is to be understood that the alkenyl units formed by R⁷ together with R⁸ are directly attached to the bridged cyclohexane ring by a double bond.

When present, the optional substituents on alkenyl or alkynyl include those optional substituents given above for an alkyl moiety.

Halogen is fluorine, chlorine, bromine or iodine.

Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF₃, CF₂C₁, CF₂H, CCl₂H, FCH₂, ClCH₂, BrCH₂, CH₃CHF, (CH₃)₂CF, CF₃CH₂ or CHF₂CH₂.

In the context of the present specification the term “aryl” refers to ring systems which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl.

The term “heteroaryl” preferably refers to an aromatic ring system containing at least one heteroatom and consisting either of a single ring or of two or more fused rings. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulphur. Examples of such groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, benzofuryl, benzisofuryl, benzothienyl, benzisothienyl, indolyl, isoindolyl, indazolyl, benzothiazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, 2,1,3-benzoxadiazole, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, benzotriazinyl, purinyl, pteridinyl and indolizinyl.

Preferred examples of heteroaromatic radicals include pyridyl, pyrimidinyl, triazinyl, thienyl, furyl, oxazolyl, isoxazolyl, 2,1,3-benzoxadiazolyl and thiazolyl.

Another group of preferred heteroaryls comprises furyl, thienyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl or quinoxalinyl.

The term “heterocyclyl” preferably refers to a non-aromatic preferably monocyclic or bicyclic ring systems containing up to 7 atoms including one or more (preferably one or two) heteroatoms selected from O, S and N. Examples of such rings include 1,3-dioxolane, oxetane, tetrahydrofuran, morpholine, thiomorpholin and piperazine. When present, the optional substituents on heterocyclyl include C₁₋₆ alkyl and C₁₋₆ haloalkyl as well as those optional substituents given above for an alkyl moiety.

Cycloalkyl includes preferably cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Cycloalkylalkyl is preferentially cyclopropylmethyl. Cycloalkenyl includes preferably cyclopentenyl and cyclohexenyl. When present, the optional substituents on cycloalkyl or cycloalkenyl include C₁₋₃ alkyl as well as those optional substituents given above for an alkyl moiety.

Carbocyclic rings such as those formed by R⁷ together with R⁸ include aryl, cycloalkyl or carbocyclic groups, and cycloalkenyl groups.

When present, the optional substituents on aryl, heteroaryl and carbocycles are preferably selected independently, from halogen, nitro, cyano, rhodano, isothiocyanato, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy-(C₁₋₆)alkyl, C₂₋₆ alkenyl, C₂₋₄ haloalkenyl, C₂₋₄ alkynyl, C₃₋₇ cycloalkyl (itself optionally substituted with C₁₋₆ alkyl or halogen), C₅₋₇ cycloalkenyl (itself optionally substituted with C₁₋₆ alkyl or halogen), hydroxy, C₁₋₁₀ alkoxy, C₁₋₁₀ alkoxy(C₁₋₁₀)alkoxy, tri(C₁₋₄)alkylsilyl(C₁₋₄)alkoxy, C₁₋₆ alkoxycarbonyl(C₁₋₁₀)alkoxy, C₁₋₁₀ haloalkoxy, aryl(C₁₋₄)alkoxy (where the aryl group is optionally substituted with halogen or C₁₋₆ alkyl), C₃₋₇ cycloalkyloxy (where the cycloalkyl group is optionally substituted with C₁₋₆ alkyl or halogen), C₃₋₁₀ alkenyloxy, C₃₋₁₀ alkynyloxy, mercapto, C₁₋₁₀ alkylthio, C₁₋₁₀ haloalkylthio, aryl(C₁₋₄)alkylthio, C₃₋₇ cycloalkylthio (where the cycloalkyl group is optionally substituted with C₁₋₆ alkyl or halogen), tri(C₁₋₄)-alkylsilyl(C₁₋₆)alkylthio, arylthio, C₁₋₄ alkylsulfonyl, C₁₋₆ haloalkylsulfonyl, C₁₋₆ alkylsulfinyl, C₁₋₆ haloalkylsulfinyl, arylsulfonyl, tri(C₁₋₄)alkylsilyl, aryldi(C₁₋₄)-alkysilyl, (C₁₋₄)alkyldiarylsilyl, triarylsilyl, C₁₋₁₀ alkylcarbonyl, HO₂C, C₁₋₁₀ alkoxycarbonyl, aminocarbonyl, C₁₋₆ alkylaminocarbonyl, di(C₁₋₆ alkyl)-aminocarbonyl, N—(C₁₋₃ alkyl)-N—(C₁₋₃ alkoxy)aminocarbonyl, C₁₋₆ alkylcarbonyloxy, arylcarbonyloxy, di(C₁₋₆)alkylamino-carbonyloxy, aryl (itself optionally substituted with C₁₋₆ alkyl or halogen), heteroaryl (itself optionally substituted with C₁₋₆ alkyl or halogen), heterocyclyl (itself optionally substituted with C₁₋₆ alkyl or halogen), aryloxy (where the aryl group is optionally substituted with C₁₋₆ alkyl or halogen), heteroaryloxy (where the heteroaryl group is optionally substituted with C₁₋₆ alkyl or halogen), heterocyclyloxy (where the heterocyclyl group is optionally substituted with C₁₋₆ alkyl or halogen), amino, C₁₋₆ alkylamino, di(C₁₋₆)alkylamino, C₁₋₆ alkylcarbonylamino, N—(C₁₋₆)alkylcarbonyl-N—(C₁₋₆)alkylamino, arylcarbonyl, (where the aryl group is itself optionally substituted with halogen or C₁₋₆ alkyl) or two adjacent positions on an aryl or heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen or C₁₋₆ alkyl. Further substituents for aryl or heteroaryl include arylcarbonylamino (where the aryl group is substituted by C₁₋₆ alkyl or halogen), (C₁₋₆)alkoxycarbonylamino(C₁₋₆)alkoxycarbonyl-N—(C₁₋₆)alkylamino, aryloxycarbonylamino (where the aryl group is substituted by C₁₋₆ alkyl or halogen), aryloxycarbonyl-N—(C₁₋₆)alkylamino, (where the aryl group is substituted by C₁₋₆ alkyl or halogen), arylsulphonylamino (where the aryl group is substituted by C₁₋₆ alkyl or halogen), arylsulphonyl-N—(C₁₋₆)alkylamino (where the aryl group is substituted by C₁₋₆ alkyl or halogen), aryl-N—(C₁₋₆)alkylamino (where the aryl group is substituted by C₁₋₆ alkyl or halogen), arylamino (where the aryl group is substituted by C₁₋₆ alkyl or halogen), heteroaryl amino (where the heteroaryl group is substituted by C₁₋₆ alkyl or halogen), heterocyclylamino (where the heterocyclyl group is substituted by C₁₋₆ alkyl or halogen), aminocarbonylamino, C₁₋₆ alkylaminocarbonylamino, di(C₁₋₆)alkylaminocarbonylamino, arylaminocarbonylamino where the aryl group is substituted by C₁₋₆ alkyl or halogen), aryl-N—(C₁₋₆)alkylamino-carbonylamino where the aryl group is substituted by C₁₋₆ alkyl or halogen), C₁₋₆ alkylaminocarbonyl-N—(C₁₋₆)alkylamino, di(C₁₋₆)alkylaminocarbonyl-N—(C₁₋₆)alkylamino, arylaminocarbonyl-N—(C₁₋₆)alkylamino where the aryl group is substituted by C₁₋₆ alkyl or halogen) and aryl-N—(C₁₋₆)alkylaminocarbonyl-N—(C₁₋₆)alkylamino where the aryl group is substituted by C₁₋₆ alkyl or halogen).

For substituted heterocyclyl groups it is preferred that one or more substituents are independently selected from halogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆ alkylsulfonyl, nitro and cyano. It is to be understood that dialkylamino substituents include those where the dialkyl groups together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which is optionally substituted by one or two independently selected (C₁₋₆)alkyl groups. When heterocyclic rings are formed by joining two groups on an N atom, the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two independently selected (C₁₋₆) alkyl groups.

It should be understood that the term “substituent” in the definitions of R⁶ to R¹¹ comprises preferably all substitutents given above for “aryl”, “heteroaryl” and “heterocyclyl”.

The invention relates also to the salts which the compounds of formula I are able to form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.

Among the alkali metal and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium. The compounds of formula I according to the invention also include hydrates which may be formed during the salt formation.

Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C₁-C₁₈alkylamines, C₁-C₄hydroxyalkylamines and C₂-C₄-alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-but-2-enylamine, n-pent-2-enylamine, 2,3-dimethylbut-2-enylamine, dibut-2-enylamine, n-hex-2-enylamine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.

Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(R_(a)R_(b)R_(c)R_(d))]OH wherein R_(a), R_(b), R_(c) and R_(d) are each independently of the others C₁-C₄alkyl. Further suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.

The latentiating groups G are selected to allow its removal by one or a combination of biochemical, chemical or physical processes to afford compounds of formula I where G is H before, during or following application to the treated area or plants. Examples of these processes include enzymatic cleavage, chemical hydrolysis and photoloysis. Compounds bearing such groups G may offer certain advantages, such as improved penetration of the cuticula of the plants treated, increased tolerance of crops, improved compatibility or stability in formulated mixtures containing other herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides, or reduced leaching in soils.

Preferably, in the compounds of the formula I, R⁶ and R¹¹ are independently of each other hydrogen, halogen, formyl, cyano or nitro or

R⁶ and R¹¹ are independently of each other C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₆alkoxy, C₃-C₇ cycloalkyl, C₃-C₇ cycloalkenyl, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, or R⁶ and R¹¹ are independently of each other a group COR¹³, CO₂R¹⁴ or CONR¹⁵R¹⁶, CR¹⁷═NOR¹⁸, CR¹⁹═NNR²⁰R²¹, NHR²², NR²²R²³ or OR²⁴, wherein R¹³ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, R¹⁴ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, phenyl, heteroaryl or is 3-7 membered heterocyclyl, where all these substituents are optionally substituted, R¹⁵ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, R¹⁶ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, C₁-C₆alkylsulfonyl, phenylsulfonyl, heteroarylsulfonyl, amino, C₁-C₆alkylamino, diC₁-C₆alkylamino, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, or R¹⁵ and R¹⁶ may be joined to form an optionally substituted 3-7 membered ring, optionally containing an oxygen, sulfur or nitrogen atom, R¹⁷ and R¹⁹ are independently of each other hydrogen, C₁-C₃alkyl or C₃-C₆cycloalkyl, R¹⁸, R²⁰ and R²¹ are independently of each other hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, aminocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, phenyl or heteroaryl, where all these substituents are optionally substituted, R²² is C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, C₁-C₆alkylsulfonyl, phenylcarbonyl, phenoxycarbonyl, phenylaminocarbonyl, phenylthiocarbonyl, phenylsulfonyl, heteroarylcarbonyl, heteroaryloxycarbonyl, heteroarylaminocarbonyl, heteroarylthiocarbonyl or heteroarylsulfonyl, where all these substituents are optionally substituted, R²³ is C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, C₁-C₆alkylsulfonyl, phenyl or heteroaryl, where all these substituents are optionally substituted, or R²² and R²³ may be joined to form an optionally substituted 3-7 membered ring, optionally containing an oxygen, sulfur or nitrogen atom, where all these substituents are optionally substituted, and R²⁴ is C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, aminocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, tri(C₁-C₆alkyl)silyl, phenyl or heteroaryl, where all these substituents are optionally substituted.

More preferably, R⁶ and R¹¹ are independently of each other hydrogen, halogen, cyano, optionally substituted C₁-C₆alkyl or a group COR¹³, CO₂R¹⁴ or CONR¹⁵R¹⁶, CR¹⁷═NOR¹⁸ or CR¹⁹═NNR²⁰R²¹, wherein

R¹³, R¹⁴, R¹⁵ and R¹⁶ are C₁-C₆alkyl, R¹⁷ and R¹⁹ are hydrogen or C₁-C₃ alkyl, R¹⁸ is C₁-C₃ alkyl, and R²⁰ and R²¹ are independently of each other hydrogen or C₁-C₃alkyl. In particular, R⁶ and R¹¹ are independently of each other hydrogen, methyl or methyl substituted by C₁-C₃alkoxy.

Preferably, R⁷, R⁸, R⁹ and R¹⁰ are independently of each other hydrogen, halogen, hydroxyl, formyl, amino, cyano or nitro, or

R⁷, R⁸, R⁹ and R¹⁰ are independently of each other C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆alkoxyC₁-C₆alkyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆alkylthioC₁-C₆alkyl, C₁-C₆alkylsulfinylC₁-C₆alkyl, C₁-C₆alkylsulfonylC₁-C₆alkyl, C₃-C₇ cycloalkyl, C₄-C₇cycloalkenyl, tri(C₁-C₆alkyl)silyl, aryl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, or R⁷, R⁸, R⁹ and R¹⁰ are independently of each other a group COR¹³, CO₂R¹⁴ or CONR¹⁵R¹⁶, CR¹⁷═NOR¹⁸, CR¹⁹═NNR²⁰R²¹, NR²²R²³ or OR²⁴, wherein R¹³ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, R¹⁴ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, phenyl, heteroaryl or is 3-7 membered heterocyclyl, where all these substituents are optionally substituted, R¹⁵ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, R¹⁶ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, C₁-C₆alkylsulfonyl, amino, C₁-C₆alkylamino, diC₁-C₆alkylamino, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, or R¹⁵ and R¹⁶ may be joined to form an optionally substituted 3-7 membered ring, optionally containing an oxygen, sulfur or nitrogen atom, R¹⁷ and R¹⁹ are independently of each other hydrogen, C₁-C₃alkyl or C₃-C₆cycloalkyl, R¹⁸, R²⁰ and R²¹ are independently of each other hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, phenyl or heteroaryl, where all these substituents are optionally substituted, R²² and R²³ are independently of each other C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, C₁-C₆alkylsulfonyl, phenyl or heteroaryl or R²² and R²³ may be joined to form an optionally substituted 3-7 membered ring, optionally containing an oxygen, sulfur or nitrogen atom, where all these substituents are optionally substituted, and R²⁴ is C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, C₁-C₆alkylsulfonyl, tri(C₁-C₆alkyl)silyl, phenyl or heteroaryl, where all these substituents are optionally substituted.

More preferably, R⁷, R⁸, R⁹ and R¹⁰ are hydrogen.

It is also preferred that one of R⁷, R⁸, R⁹ and R¹⁰ is methyl or ethyl.

It is also preferred that one of R⁷, R⁸, R⁹ and R¹⁰ is an optionally substituted aryl or heteroaryl and more preferably optionally substituted phenyl, naphthyl, furyl, thienyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl or quinoxalinyl.

In particular, one of R⁷, R⁸, R⁹ and R¹⁰ is pyridyl or pyridyl substituted by trifluoromethyl or halogen.

It is also preferred that R⁷ and R¹⁰ form a bond.

Preferably, R⁷, R⁸, R⁹ and R¹⁰ are independently of each other hydrogen, cyano, C₁-C₆alkyl, C₂-C₆alkenyl, C₁-C₆alkoxy, C₁-C₆alkoxyC₁-C₆alkyl, C₁-C₆alkylthioC₁-C₆alkyl, C₁-C₆alkylsulfinylC₁-C₆alkyl, C₁-C₆alkylsulfonylC₁-C₆alkyl, 3-7 membered heterocyclyl, optionally substituted phenyl or optionally substituted heteroaryl, or CR¹⁷═NOR¹⁸, wherein

R¹⁷ is hydrogen or C₁-C₃ alkyl and R¹⁸ is C₁-C₃ alkyl.

In another group of preferred compounds of the formula I, R⁷ and R⁸, or R⁹ and R¹⁰, together form a unit ═O, or form a unit ═CR²⁵R²⁶, or form a unit ═NR²⁷, or any two of R⁷, R⁸, R⁹ and R¹⁰ form a 3-8 membered ring, optionally containing a heteroatom selected from O, S or N and optionally substituted by C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃haloalkyl, halogen, phenyl, phenyl substituted by C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl, aminocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, halogen, cyano or by nitro, heteroaryl or heteroaryl substituted by C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylcarbonyl, halogen, cyano or by nitro, wherein

R²⁵ and R²⁶ are independently of each other hydrogen, halogen, cyano or nitro, or R²⁵ and R²⁶ are independently of each other C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkylamino, diC₁-C₆alkylamino, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, N-phenyl-N—C₁-C₆alkylaminocarbonyl, N-phenylC₁-C₆alkyl-N—C₁-C₆alkylaminocarbonyl, N-heteroaryl-N—C₁-C₆alkylaminocarbonyl, N-heteroarylC₁-C₆alkyl-N—C₁-C₆alkylaminocarbonyl, phenyl, heteroaryl, C₃-C₆cycloalkyl or 3-7 membered heterocyclyl, where all these substituents are optionally substituted, or R²⁵ and R²⁶ may be joined together to form a 5-8 membered ring optionally containing a heteroatom selected from O, S or N and optionally substituted by C₁-C₂alkyl or C₁-C₂alkoxy, R²⁷ is nitro or cyano, or R²⁷ is C₁-C₆alkylamino, diC₁-C₆alkylamino, C₁-C₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, phenoxy, phenylamino, N-phenyl-N—C₁-C₆alkylamino, N-phenylC₁-C₆alkyl-N—C₁-C₆alkylamino heteroaryloxy, heteroarylamino, N-heteroaryl-N—C₁-C₆alkylamino or N-heteroarylC₁-C₆alkyl-N—C₁-C₆alkylamino, where all these substituents are optionally substituted, where, more preferably, R⁷ and R⁸, or R⁹ and R¹⁰, together form a unit ═O or ═NR²⁷, wherein R²⁷ is C₁₋₃alkoxy or C₂-C₃ alkenyloxy.

More preferably, R⁷, R⁸, R⁹ and R¹⁰ are independently of each other hydrogen, cyano, C₁-C₆alkyl, C₂-C₆alkenyl, C₁-C₆alkoxy, C₁-C₆alkoxyC₁-C₆alkyl, 3-7 membered heterocyclyl, optionally substituted phenyl or optionally substituted heteroaryl.

In particular, R⁷, R⁸, R⁹ and R¹⁰ are independently of each other hydrogen, methyl, ethyl or optionally substituted phenyl.

In particular, one of R⁷, R⁸, R⁹ and R¹⁰ is optionally substituted heteroaryl, preferably optionally substituted furyl, thienyl, pyrazolyl, 1,2,4-triazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl or quinoxalinyl,

and more preferably pyridyl substituted once or twice by trifluoromethyl or halogen.

In another group of preferred compounds of the formula I, R¹, R² and R⁴ are methyl and R³ is hydrogen.

In another group of preferred compounds of the formula I, R¹, R² and R⁴ are methyl and R³ is hydrogen, and

R⁷, R⁸, R⁹ and R¹⁰ are independently of each other hydrogen, cyano, C₁-C₆alkyl, C₂-C₆alkenyl, C₁-C₆alkoxy, C₁-C₆alkoxyC₁-C₆alkyl, 3-7 membered heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, preferably optionally substituted heteroaryl, and in particular pyridyl substituted once or twice by trifluoromethyl or halogen.

In another group of preferred compounds of the formula I, R⁵ and R¹² are independently of each other hydrogen or C₁-C₃alkyl, where hydrogen is more preferred.

In another group of preferred compounds of the formula I, R¹ is methyl, ethyl, vinyl, ethynyl, cyclopropyl, difluoromethoxy, trifluoromethoxy or C₁-C₂ alkoxy and

R², R³ and R⁴ are independently of each other hydrogen, methyl, ethyl, vinyl or ethynyl.

Preferably in this group, R¹ is ethyl and R², R³ and R⁴ are independently of each other hydrogen, methyl or ethyl.

Preferably in this group, R¹, R² and R⁴ are methyl and R³ is hydrogen.

The latentiating group G is preferably selected from the groups C₁-C₈ alkyl, C₂-C₈ haloalkyl, phenylC₁-C₈alkyl (wherein the phenyl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃ alkylsulfonyl, halogen, cyano or by nitro), heteroarylC₁-C₈alkyl (wherein the heteroaryl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃ alkylsulfonyl, halogen, cyano or by nitro), C₃-C₈ alkenyl, C₃-C₈ haloalkenyl, C₃-C₈ alkynyl, C(X^(a))—R^(a), C(X^(b))—X^(c)—R^(b), C(X^(d))—N(R^(c))—R^(d), —SO₂—R^(e), —P(X^(e))(R^(f))—R^(g) or CH₂—X^(f)—R^(h) wherein X^(a), X^(b), X^(c), X^(d), X^(e) and X^(f) are independently of each other oxygen or sulfur;

R^(a) is H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl, C₁-C₅alkylaminoC₁-C₅alkyl, C₂-C₈dialkylaminoC₁-C₅alkyl, C₃-C₇cycloalkylC₁-C₅alkyl, C₁-C₅alkoxyC₁-C₆alkyl, C₃-C₅alkenyloxyC₁-C₅alkyl, C₃-C₅alkynylC₁-C₅oxyalkyl, C₁-C₅alkylthioC₁-C₅alkyl, C₁-C₅alkylsulfinylC₁-C₅alkyl, C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₈alkylideneaminoxyC₁-C₅alkyl, C₁-C₅alkylcarbonylC₁-C₅alkyl, C₁-C₅alkoxycarbonylC₁-C₅alkyl, aminocarbonylC₁-C₅alkyl, C₁-C₅alkylaminocarbonylC₁-C₅alkyl, C₂-C₈dialkylaminocarbonylC₁-C₅alkyl, C₁-C₅alkylcarbonylaminoC₁-C₅alkyl, N—C₁-C₅alkylcarbonyl-N—C₁-C₅alkylaminoC₁-C₅alkyl, C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl (wherein the phenyl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), heteroarylC₁-C₆alkyl, (wherein the heteroaryl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl or phenyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, R^(b) is C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkynyl, C₂-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₂-C₁₀aminoalkyl, C₁-C₅alkylaminoC₁-C₅alkyl, C₂-C₈dialkylaminoC₁-C₅alkyl, C₃-C₇cycloalkylC₁-C₅alkyl, C₁-C₅alkoxyC₁-C₅alkyl, C₃-C₅alkenyloxyC₁-C₅alkyl, C₃-C₅alkynyloxyC₁-C₅alkyl, C₁-C₅alkylthioC₁-C₅alkyl, C₁-C₅alkylsulfinylC₁-C₅alkyl, C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₈alkylideneaminoxyC₁-C₆alkyl, C₁-C₅alkylcarbonylC₁-C₅alkyl, C₁-C₅alkoxycarbonylC₁-C₅alkyl, aminocarbonylC₁-C₆alkyl, C₁-C₅alkylaminocarbonylC₁-C₅alkyl, C₂-C₈dialkylaminocarbonylC₁-C₅alkyl, C₁-C₅alkylcarbonylaminoC₁-C₅alkyl, N—C₁-C₅alkylcarbonyl-N—C₁-C₅alkylaminoC₁-C₅alkyl, C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl (wherein the phenyl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), heteroarylC₁-C₅alkyl, (wherein the heteroaryl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), C₃-C₅haloalkenyl, C₃-C₆cycloalkyl, phenyl or phenyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, R^(c) and R^(d) are each independently of each other hydrogen, C₁-C₁₀alkyl, C₃-C₁₀alkenyl, C₃-C₁₀alkynyl, C₂-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl, C₁-C₅alkylaminoC₁-C₅alkyl, C₂-C₈dialkylaminoC₁-C₅alkyl, C₃-C₇cycloalkylC₁-C₅alkyl, C₁-C₅alkoxyC₁-C₅alkyl, C₃-C₅alkenyloxyC₁-C₅alkyl, C₃-C₅alkynyloxyC₁-C₅alkyl, C₁-C₅alkylthioC₁-C₅alkyl, C₂-C₅alkylsulfinylC₁-C₅alkyl, C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₈alkylideneaminoxyC₁-C₅alkyl, C₁-C₆alkylcarbonylC₁-C₅alkyl, C₁-C₆alkoxycarbonylC₁-C₅alkyl, aminocarbonylC₁-C₅alkyl, C₁-C₅alkylaminocarbonylC₁-C₅alkyl, C₂-C₈dialkylaminocarbonylC₁-C₅alkyl, C₂-C₅alkylcarbonylaminoC₁-C₅alkyl, N—C₁-C₅alkylcarbonyl-N—C₂-C₅alkylaminoalkyl, C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl (wherein the phenyl may optionally be substituted by C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₂-C₃alkylsulfonyl, halogen, cyano, or by nitro), heteroarylC₁-C₅alkyl, (wherein the heteroaryl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₂-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), C₂-C₆haloalkenyl, C₃-C₈cycloalkyl, phenyl or phenyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by C₁-C₃ alkyl, C₂-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, heteroarylamino or heteroarylamino substituted by C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, diheteroarylamino or diheteroarylamino substituted by C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, phenylamino or phenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, diphenylamino or diphenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro or C₃-C₇cycloalkylamino, di-C₃-C₇cycloalkylamino or C₃-C₇cycloalkoxy or R^(c) and R^(d) may join together to form a 3-7 membered ring, optionally containing one heteroatom selected from O or S, R^(e) is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl, C₁-C₅alkylaminoC₁-C₅alkyl, C₂-C₈dialkylaminoC₁-C₅alkyl, C₃-C₇cycloalkylC₁-C₅alkyl, C₁-C₅alkoxyC₁-C₅alkyl, C₃-C₅alkenyloxyC₁-C₅alkyl, C₃-C₅alkynyloxyC₁-C₅alkyl, C₁-C₅alkylthioC₁-C₅alkyl, C₁-C₅alkylsulfinylC₁-C₅alkyl, C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₈alkylideneaminoxyC₁-C₆alkyl, C₁-C₅alkylcarbonylC₁-C₅alkyl, C₁-C₅alkoxycarbonylC₁-C₅alkyl, aminocarbonylC₁-C₅alkyl, C₁-C₆alkylaminocarbonylC₁-C₅alkyl, C₂-C₈dialkylaminocarbonylC₁-C₅alkyl, C₁-C₅alkylcarbonylaminoC₁-C₅alkyl, N—C₁-C₅alkylcarbonyl-N—C₁-C₅alkylaminoC₁-C₅alkyl, C₃-C₈trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl (wherein the phenyl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), heteroarylC₁-C₅alkyl (wherein the heteroaryl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl or phenyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, heteroarylamino or heteroarylamino substituted by C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, diheteroarylamino or diheteroarylamino substituted by C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, phenylamino or phenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, diphenylamino, or diphenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, or C₃-C₇cycloalkylamino, diC₃-C₇cycloalkylamino or C₃-C₇cycloalkoxy, C₁-C₁₀alkoxy, C₁-C₁₀haloalkoxy, C₁-C₅alkylamino or C₂-C₅dialkylamino R^(f) and R^(g) are are each independently of each other C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀alkoxy, C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl, C₁-C₆alkylaminoC₁-C₅alkyl, C₂-C₅dialkylaminoC₁-C₅alkyl, C₃-C₇cycloalkylC₁-C₅alkyl, C₁-C₅alkoxyC₁-C₅alkyl, C₃-C₅alkenyloxyC₁-C₅alkyl, C₃-C₅alkynyloxyC₁-C₅alkyl, C₁-C₅alkylthioC₁-C₅alkyl, C₁-C₅alkylsulfinylC₁-C₅alkyl, C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₅alkylideneaminoxyC₁-C₅alkyl, C₁-C₅alkylcarbonylC₁-C₅alkyl, C₁-C₅alkoxycarbonylC₁-C₅alkyl, aminocarbonylC₁-C₅alkyl, C₁-C₅alkylaminocarbonylC₁-C₅alkyl, C₂-C₈dialkylaminocarbonylC₁-C₅alkyl, C₁-C₅alkylcarbonylaminoC₁-C₅alkyl, N—C₁-C₅alkylcarbonyl-N—C₂-C₅alkylaminoalkyl, C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl (wherein the phenyl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), heteroarylC₁-C₅alkyl (wherein the heteroaryl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl or phenyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, heteroarylamino or heteroarylamino substituted by C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, diheteroarylamino or diheteroarylamino substituted by C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, phenylamino or phenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, diphenylamino, or diphenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, or C₃-C₇cycloalkylamino, diC₃-C₇cycloalkylamino or C₃-C₇cycloalkoxy, C₁-C₁₀haloalkoxy, C₁-C₅alkylamino or C₂-C₈dialkylamino, benzyloxy or phenoxy, wherein the benzyl and phenyl groups may in turn be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, and R^(h) is C₁-C₁₀alkyl, C₃-C₁₀alkenyl, C₃-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₂-C₁₀aminoalkyl, C₁-C₅alkylaminoC₁-C₅alkyl, C₂-C₈dialkylaminoC₁-C₅alkyl, C₃-C₇cycloalkylC₁-C₅alkyl, C₁-C₅alkoxyC₁-C₅alkyl, C₃-C₅alkenyloxyC₁-C₅alkyl, C₃-C₅alkynyloxyC₁-C₅alkyl, C₁-C₅alkylthioC₁-C₅alkyl, C₁-C₅alkylsulfinylC₁-C₅alkyl, C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₈alkylideneaminoxyC₁-C₆alkyl, C₁-C₅alkylcarbonylC₁-C₅alkyl, C₁-C₅alkoxycarbonylC₁-C₅alkyl, aminocarbonylC₁-C₅alkyl, C₁-C₈alkylaminocarbonylC₁-C₈alkyl, C₂-C₈dialkylaminocarbonylC₁-C₈alkyl, C₁-C₈alkylcarbonylaminoC₁-C₈alkyl, N—C₁-C₈alkylcarbonyl-N—C₁-C₅alkylaminoC₁-C₃alkyl, C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl (wherein the phenyl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃ alkylsulfonyl, halogen, cyano or by nitro), heteroarylC₁-C₆alkyl (wherein the heteroaryl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃ alkylsulfonyl, halogen, cyano or by nitro), phenoxyC₁-C₈alkyl (wherein the phenyl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃ alkylsulfonyl, halogen, cyano or by nitro), heteroaryloxyC₁-C₈alkyl (wherein the heteroaryl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₃alkylsulfinyl, C₁-C₃ alkylsulfonyl, halogen, cyano or by nitro), C₃-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl or phenyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen or by nitro, or heteroaryl, or heteroaryl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro.

In particular, the latentiating group G is a group —C(X^(a))—R^(a) or —C(X^(b))—X^(c)—R^(b), and the meanings of X^(a), R^(a), X^(b), X^(c), X^(b) and R^(b) are as defined above.

It is preferred that G is hydrogen, an alkali metal or alkaline earth metal, where hydrogen is especially preferred.

It should be understood that in those compounds of formula I where G is a metal, ammonium (such as NH₄+; N(alkyl)₄+) or sulfonium (such as S(alkyl)₃+) cation, the corresponding negative charge is largely delocalised across the O—C═C—C═O unit.

Depending on the nature of the substituents, compounds of formula I may exist in different isomeric forms. When G is hydrogen, for example, compounds of formula I may exist in different tautomeric forms.

This invention covers all such isomers and tautomers and mixtures thereof in all proportions. Also, when substituents contain double bonds, cis- and trans-isomers can exist. These isomers, too, are within the scope of the claimed compounds of the formula I.

A compound of formula I wherein G is C₁-C₈ alkyl, C₂-C₈ haloalkyl, phenylC₁-C₈alkyl (wherein the phenyl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsufinyl, C₁-C₃ alkylsulfonyl, halogen, cyano or by nitro), heteroarylC₁-C₈alkyl (wherein the heteroaryl may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃ alkylsulfonyl, halogen, cyano or by nitro), C₃-C₈ alkenyl, C₃-C₈ haloalkenyl, C₃-C₈ alkynyl, C(X^(a))—R^(a), C(X^(b))—X^(c)—R^(b), C(X^(d))—N(R^(c))—R^(d), —SO₂—R^(e), —P(X^(e))(R^(f))—R^(g) or CH₂—X^(f)—R^(h) where X^(a), X^(b), X^(c), X^(d), X^(e), X^(f), R^(a), R^(b), R^(c), R^(d), R^(e), R^(f), R^(g) and R^(h) are as defined above may be prepared by treating a compound of formula (A), which is a compound of formula I wherein G is H, with a reagent G-Z, wherein G-Z is alkylating agent such as an alkyl halide (the definition of alkyl halides includes simple C₁-C₈ alkyl halides such as methyl iodide and ethyl iodide, substituted alkyl halides such as phenylC₁-C₆alkyl, chloromethyl alkyl ethers, Cl—CH₂—X^(f)—R^(h), wherein X^(f) is oxygen, and chloromethyl alkyl sulfides Cl—CH₂—X^(f)—R^(h), wherein X^(f) is sulfur), a C₁-C₈ alkyl sulfonate, or a di-C₁-C₈-alkyl sulfate, or with a C₃-C₈ alkenyl halide, or with a C₃-C₈ alkynyl halide, or with an acylating agent such as a carboxylic acid, HO—C(X^(a))R^(a), wherein X^(a) is oxygen, an acid chloride, Cl—C(X^(a))R^(a), wherein X^(a) is oxygen, or acid anhydride, [R^(a)C(X^(a))]₂O, wherein X^(a) is oxygen, or an isocyanate, R^(c)N═C═O, or a carbamoyl chloride, Cl—C(X^(d))—-N(R^(c))—R^(d) (wherein X^(d) is oxygen and with the proviso that neither R^(c) or R^(d) is hydrogen), or a thiocarbamoyl chloride, Cl—C(X^(d))—N(R^(d))—R^(d) (wherein X^(d) is sulfur and with the proviso that neither R^(c) or R^(d) is hydrogen) or a chloroformate, Cl—C(X^(b))—X^(c)—R^(b), (wherein X^(b) and X^(c) are oxygen), or a chlorothioformate Cl—C(X^(b))—X^(c)—R^(b) (wherein X^(b) is oxygen and X^(c) is sulfur), or a chlorodithioformate Cl—C(X^(b))—X^(c)—R^(b), (wherein X^(b) and X^(c) are sulfur), or an isothiocyanate, R^(c)N═C═S, or by sequential treatment with carbon disulfide and an alkylating agent, or with a phosphorylating agent such as a phosphoryl chloride, Cl—P(X^(e))(R^(f))—R^(g) or with a sulfonylating agent such as a sulfonyl chloride Cl—SO₂—R^(e), preferably in the presence of at least one equivalent of base.

Depending on the nature of the substituents R¹ to R¹², and of the group G, isomeric compounds of formula I may be formed. For example, a compound of formula (A) wherein R⁵ and R¹² are different may give rise to a compound of formula (1a) or to a compound of formula (1b), or to a mixture of compounds of formula (1a) and formula (1b).

The O-alkylation of cyclic 1,3-diones is known; suitable methods are described, for example, by T. Wheeler U.S. Pat. No. 4,436,666. Alternative procedures have been reported by M. Pizzorno and S. Albonico, Chem. Ind. (London), (1972), 425; H. Born et al., J. Chem. Soc., (1953), 1779; M. Constantino et al., Synth. Commun., (1992), 22 (19), 2859; Y. Tian et al., Synth. Commun., (1997), 27 (9), 1577, S. Chandra Roy et al., Chem. Letters, (2006), 35 (1), 16, and P. Zubaidha et al., Tetrahedron Lett., (2004), 45, 7187.

The O-acylation of cyclic 1,3-diones may be effected by procedures similar to those described, for example, by R. Haines, U.S. Pat. No. 4,175,135, and by T. Wheeler, U.S. Pat. No. 4,422,870, U.S. Pat. No. 4,659,372 and U.S. Pat. No. 4,436,666. Typically diones of formula (A) may be treated with the acylating agent in the presence of at least one equivalent of a suitable base, optionally in the presence of a suitable solvent. The base may be inorganic, such as an alkali metal carbonate or hydroxide, or a metal hydride, or an organic base such as a tertiary amine or metal alkoxide. Examples of suitable inorganic bases include sodium carbonate, sodium or potassium hydroxide, sodium hydride, and suitable organic bases include trialkylamines, such as trimethylamine and triethylamine, pyridines or other amine bases such as 1,4-diazobicyclo[2.2.2]octane and 1,8-diazabicyclo[5.4.0]undec-7-ene. Preferred bases include triethylamine and pyridine. Suitable solvents for this reaction are selected to be compatible with the reagents and include ethers such as tetrahydrofuran and 1,2-dimethoxyethane and halogenated solvents such as dichloromethane and chloroform. Certain bases, such as pyridine and triethylamine, may be employed successfully as both base and solvent. For cases where the acylating agent is a carboxylic acid, acylation is preferably effected in the presence of a coupling agent such as 2-chloro-1-methylpyridinium iodide, N, N′-dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and N,N′-carbodiimidazole, and optionally a base such as triethylamine or pyridine in a suitable solvent such as tetrahydrofuran, dichloromethane or acetonitrile. Suitable procedures are described, for example, by W. Zhang and G. Pugh, Tetrahedron Lett., (1999), 40 (43), 7595-7598 and T. Isobe and T. Ishikawa, J. Org. Chem., (1999), 64 (19), 6984.

Phosphorylation of cyclic 1,3-diones may be effected using a phosphoryl halide or thiophosphoryl halide and a base by procedures analogous to those described by L. Hodakowski, U.S. Pat. No. 4,409,153.

Sulfonylation of a compound of formula (A) may be achieved using an alkyl or aryl sulfonyl halide, preferably in the presence of at least one equivalent of base, for example by the procedure of C. Kowalski and K. Fields, J. Org. Chem., (1981), 46, 197.

A compound of formula (A) may be prepared by the cyclisation of a compound of formula (B), wherein R is hydrogen or an alkyl group, preferably in the presence of an acid or base, and optionally in the presence of a suitable solvent, by analogous methods to those described by T. Wheeler, U.S. Pat. No. 4,209,532. The compounds of formula (B) have been particularly designed as intermediates in the synthesis of the compounds of the formula I. A compound of formula (B) wherein R is hydrogen may be cyclised under acidic conditions, preferably in the presence of a strong acid such as sulfuric acid, polyphosphoric acid or Eaton's reagent, optionally in the presence of a suitable solvent such as acetic acid, toluene or dichloromethane.

A compound of formula (B) wherein R is alkyl (preferably methyl or ethyl), may be cyclised under acidic or basic conditions, preferably in the presence of at least one equivalent of a strong base such as potassium tert-butoxide, lithium diisopropylamide or sodium hydride and in a solvent such as tetrahydrofuran, toluene, dimethylsulfoxide or N,N-dimethylformamide.

A compound of formula (B), wherein R is H, may be prepared by saponification of a compound of formula (C) wherein R′ is alkyl (preferably methyl or ethyl), under standard conditions, followed by acidification of the reaction mixture to effect decarboxylation, by similar processes to those described, for example, by T. Wheeler, U.S. Pat. No. 4,209,532.

A compound of formula (B), wherein R is H, may be esterified to a compound of formula (B), wherein R is alkyl, under standard conditions, for example by heating with an alkyl alcohol, ROH, in the presence of an acid catalyst.

A compound of formula (C), wherein R is alkyl, may be prepared by treating a compound of formula (D) with a suitable carboxylic acid chloride of formula (E) under basic conditions. Suitable bases include potassium tert-butoxide, sodium bis(trimethylsilyl)amide and lithium diisopropylamide and the reaction is preferably conducted in a suitable solvent (such as tetrahydrofuran or toluene) at a temperature of between −80° C. and 30° C. Alternatively, a compound of formula (C), wherein R is H, may be prepared by treating a compound of formula (D) with a suitable base (such as potassium tert-butoxide, sodium bis(trimethylsilyl)amide and lithium diisopropylamide) in a suitable solvent (such as tetrahydrofuran or toluene) at a suitable temperature (between −80° C. and 30° C.) and reacting the resulting anion with a suitable anhydride of formula (F):

Compounds of formula (D) are known compounds, or may be prepared from known compounds by known methods.

A compound of formula (E) may be prepared from a compound of formula (F) by treatment with an alkyl alcohol, R—OH, in the presence of a base, such as dimethylaminopyridine or an alkaline metal alkoxide (see, for example, S. Buser and A. Vasella, Helv. Chim. Acta, (2005), 88, 3151, M. Hart et al., Bioorg. Med. Chem. Letters, (2004), 14, 1969), followed by treatment of the resulting acid with a chlorinating reagent such as oxalyl chloride or thionyl chloride under known conditions (see, for example, C. Santelli-Rouvier. Tetrahedron Lett., (1984), 25 (39), 4371; D. Walba and M. Wand, Tetrahedron Lett., (1982), 23 (48), 4995; J. Cason, Org. Synth. Coll. Vol. III, (169), 1955).

A compound of formula (F) wherein R⁷ and R¹⁰ are hydrogen may be prepared by the reduction of a compound of formula (G) under known conditions (see, for example, Y. Baba, N. Hirukawa and M. Sodeoka, Bioorg. Med. Chem. (2005), 13 (17), 5164, M. Hart et al., Bioorg. Med. Chem. Letters, (2004), 14 (18), 1969, Y. Baba, N. Hirukawa, N. Tanohira and M. Sodeoka, J. Am. Chem. Soc., (2003), 125, 9740).

A compound of formula (G) may be prepared by reacting a compound of formula (H) with an anhydride of formula (J), optionally in the presence of a Lewis acid catalyst, and according to procedures described, for example, by O. Diels and K. Alder, Liebigs Ann. Chem., (1931), 490, 257, K. Potts and E. Walsh, J. Org. Chem., (1984), 49 (21), 4099, J. Jurczak, T. Kozluk, S. Filipek and S. Eugster, Helv. Chim. Acta, (1982), 65, 1021, W. Dauben, C. Kessel and K. Takemura, J. Am. Chem. Soc., (1980), 102, 6893, A. Pelter and B. Singaram, Tetrahedron Lett., (1982), 23, 245, M. Lee and C. Hemdon, J. Org. Chem., (1978), 43, 518, B. Fisher and J. Hodge, J. Org. Chem. (1964), 29, 776, G. D'Alelio, C. Williams and C. Wilson, J. Org. Chem., (1960), 25, 1028, Z. Song, M. Ho and H. Wong, J. Org. Chem., (1994), 59 (14), 3917-3926, W. Tochtermann, S. Bruhn and C. Wolff, Tetrahedron Lett., (1994), 35(8), 1165, W. Dauben, J. Lam and Z. Guo, J. Org. Chem., (1996), 61 (14), 4816, M. Sodeoka, Y. Baba, S. Kobayashi and N. Hirukawa, Bioorg. Med. Chem. Lett., (1997), 7 (14), 1833, M. Avalos, R. Babiano, J. Bravo, P. Cintas, J. Jimenez and J. Palacios, Tetrahedron Lett., (1998), 39(50), 9301, J. Auge, R. Gil, S. Kalsey and N. Lubin-Germain, Synlett, (2000), 6, 877, I. Hemeon, C. Deamicis, H. Jenkins, P. Scammells and R. Singer, Synlett, (2002), 11, 1815, M. Essers, B. Wibbeling and G. Haufe, Tetrahedron Lett., (2001), 42 (32), 5429, P. Vogel et al., Tetrahedron Asymmetry, (1996), 7 (11), 3153, Y. Baba, N. Hirukawa, N. Tanohira and M. Sodeoka, J. Am. Chem. Soc., (2003), 125, 9740, L. Ghosez et al., Tetrahedron Lett., (1988), 29 (36), 4573, H. Kotsuki, S. Kitagawa and H. Nishizawa, J. Org. Chem., (1978), 43 (7), 1471, Y. Li et al., J. Org. Chem., (1997), 62 (23), 7926, M. Drew et al., J. Chem. Soc. Perkin Trans. 1, (1985), 1277, R. McDonald and C. Reineke, J. Org. Chem., (1967), 32, 1878, R. Fleming and B. Murray, J. Org. Chem., (1979), 44 (13), 2280, M. Goldstein and G. Thayer Jr. J. Am. Chem. Soc., (1965), 87 (9), 1925 and G. Keglevich et al., J. Organomet. Chem., (1999), 579, 182, and references therein.

-   -   Compounds of formula (H) and formula (J) are known compounds, or         may be made from known compounds by known methods.

Compounds of formula (G) are alkenes, and as such undergo further reactions typical of alkenes to give additional compounds of formula (F) according to known procedures. Examples of such reactions include, but are not restricted to, halogenation, epoxidation, cyclopropanation, dihydroxylation, hydroarylation, hydrovinylation and hydration of alkenes. In turn, the products from these reactions may be transformed into additional compounds of formula (F) by methods described, for example by J. March, Advanced Organic Chemistry, third edition, John Wiley and Sons. Compounds of formula (G) wherein R⁸ or R⁹ are C₁-C₆alkoxy are enol ethers, and these may be hydrolysed to the corresponding ketone using standard procedures to give additional compounds of formula (F). Certain compounds of formula (F), for example where R⁷ is a halogen, may be converted into compounds of formula (G) by known methods.

A compound of formula (G) may also be prepared by reacting a compound of formula (H) with a compound of formula (K), wherein R″ is hydrogen or an alkyl group, to give a compound of formula (L) and cyclising a compound of formula (L) under known conditions (see, for example, P. Sprague et al., J. Med. Chem., (1985), 28, 1580, A. Guzaev and M. Manoharan, J. Am. Chem. Soc., (2003), 125, 2380, and A. Marchand and R. Allen, J. Org. Chem., (1975), 40 (17), 2551.

A compound of formula (L) may also be reduced to a compound of formula (M), and a compound of formula (M) cyclised to a compound of formula (F) wherein R⁷ and R¹⁰ are hydrogen, under conditions similar to those described previously.

Compounds of formula (K) are known compounds, or may be prepared from known compounds by known methods.

Additional compounds of formula (A) may be prepared by reacting an iodonium ylide of formula (N), wherein Ar is an optionally substituted phenyl group, and an aryl boronic acid of formula (O), in the presence of a suitable palladium catalyst, a base and in a suitable solvent.

Suitable palladium catalysts are generally palladium(II) or palladium(0) complexes, for example palladium(II)dihalides, palladium(II)acetate, palladium(II) sulfate, bis(triphenylphosphine)-palladium(II) dichloride, bis(tricyclopentylphosphine)palladium(II)dichloride, bis(tricyclohexyl-phosphine)palladium(II) dichloride, bis(dibenzylideneacetone)palladium(0) or tetrakis-(triphenylphosphine)palladium(0). The palladium catalyst can also be prepared “in situ” from palladium(II) or palladium(0) compounds by complexing with the desired ligands, by, for example, combining the palladium(II) salt to be complexed, for example palladium(II)dichloride (PdCl₂) or palladium(II)acetate (Pd(OAc)₂), together with the desired ligand, for example triphenyl-phosphine (PPh₃), tricyclopentylphosphine, tricyclohexylphosphine, 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl or 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl and the selected solvent, with a compound of formula (N), the arylboronic acid of formula (O), and a base. Also suitable are bidendate ligands, for example 1,1′-bis(diphenylphosphino)ferrocene or 1,2-bis(diphenylphosphino)ethane. By heating the reaction medium, the palladium(II) complex or palladium(0) complex desired for the C—C coupling reaction is thus formed “in situ”, and then initiates the C—C coupling reaction.

The palladium catalysts are used in an amount of from 0.001 to 50 mol %, preferably in an amount of from 0.1 to 15 mol %, based on the compound of formula (N). The reaction may also be carried out in the presence of other additives, such as tetralkylammonium salts, for example, tetrabutylammonium bromide. Preferably the palladium catalyst is palladium acetate, the base is lithium hydroxide and the solvent is aqueous 1,2-dimethoxyethane.

A compound of formula (N) may be prepared from a compound of formula (P) by treatment with a hypervalent iodine reagent such as a (diacetoxy)iodobenzene or an iodosylbenzene and a base such as aqueous sodium carbonate, lithium hydroxide or sodium hydroxide in a solvent such as water or an aqueous alcohol such as aqueous ethanol according to the procedures of K. Schank and C. Lick, Synthesis, (1983), 392, R. M. Moriarty et al., J. Am. Chem. Soc, (1985), 107, 1375, or of Z. Yang et al., Org. Lett., (2002), 4 (19), 3333.

A compound of formula (P) wherein R⁷ and R¹⁰ are hydrogen may be prepared by reduction of a compound of formula (Q) under known conditions.

Compounds of formula (R) are alkenes, and as such undergo further reactions typical of alkenes to give additional compounds of formula (P) according to known procedures. Examples of such reactions include, but are not restricted to, halogenation, epoxidation, cyclopropanation, dihydroxylation, hydroarylation, hydrovinylation and hydration of alkenes. In turn, the products of these reactions may be transformed into additional compounds of formula (P) by methods described, for example by J. March, Advanced Organic Chemistry, third edition, John Wiley and Sons. Compounds of formula (R) wherein R⁸ or R⁹ are C₁-C₆alkoxy are enol ethers, and these may be hydrolysed to the corresponding ketone using standard procedures. In turn, the ketone may be further transformed, for example by ketalisation, oximation, reduction and the like under known conditions to give additional compounds of formula (P).

A compound of formula (R) may be prepared by reacting a compound of formula (S) with a cyclopentenedione of formula (T), optionally in the presence of a Lewis acid catalyst, according to procedures described, for example by B. Zwanenburg et al., Tetrahedron (1989), 45 (22), 7109 and by M. Oda et al., Chem. Lett., (1977), 307.

Compounds of formula (H) and formula (T) are known compounds or may be made from known compounds by known methods.

In a further approach, a compound of formula (A) may be prepared from a compound of formula I, wherein G is C₁₋₄ alkyl, by hydrolysis, preferably in the presence of an acid catalyst such as hydrochloric acid and optionally in the presence of a suitable solvent such as tetrahydrofuran, acetone or 4-methylpentan-2-one.

A compound of formula I wherein G is C₁₋₄ alkyl, may be prepared from a compound of formula (U), wherein G is C₁₋₄ alkyl, and Hal is a halogen (preferably bromine or iodine), by coupling with an aryl boronic acid of formula (O), in the presence of a suitable palladium catalyst and a base and preferably in the presence of a suitable ligand, and in a suitable solvent. Preferably the palladium catalyst is palladium acetate, the base is potassium phosphate, the ligand is 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl and the solvent is toluene.

A compound of formula (U) may be prepared by halogenation of a compound of formula (P), followed by reaction of the resulting halide of formula (V) with a C₁₋₄ alkyl halide or tri-C₁₋₄-alkylorthoformate under known conditions (for example by the procedures of R. Shepherd and A. White, J. Chem. Soc. Perkin Trans. 1 (1987), 2153, and Y.- L. Lin et at., Bioorg. Med. Chem. (2002), 10, 685). Alternatively, a compound of formula (U) may be prepared by reaction of a compound of formula (P) with a C₁₋₄ alkyl halide or a tri-C₁₋₄-alkylorthoformate, and halogenation of the resulting enone of formula (W) under known conditions.

A compound of formula (O) may be prepared from an aryl halide of formula (X), wherein Hal is bromine or iodine, by known methods (see, for example, W. Thompson and J. Gaudino, J. Org. Chem., (1984), 49, 5237 and R. Hawkins et al., J. Am. Chem. Soc., (1960), 82, 3053). For example, an aryl halide of formula (X) may be treated with an alkyl lithium or alkyl magnesium halide in a suitable solvent, preferably diethyl ether or tetrahydrofuran, at a temperature of between −80° C. and 30° C., and the aryl magnesium or aryl lithium reagent obtained may then be reacted with a trialkyl borate (preferably trimethylborate) to give an aryl dialkylboronate which may be hydrolysed to provide a boronic acid of formula (O) under acidic conditions.

Alternatively a compound of formula (X) may be reacted with a cyclic boronate ester derived from a 1,2- or a 1,3-alkanediol such as pinacol, 2,2-dimethyl-1,3-propanediol and 2-methyl-2,4-pentanediol) under known conditions (see, for example, N. Miyaura et al., J. Org. Chem., (1995), 60, 7508, and W. Zhu and D. Ma, Org. Lett., (2006), 8 (2), 261), and the resulting boronate ester may be hydrolysed under acidic conditions to give a boronic acid of formula (O). An aryl halide of formula (X) may be prepared from an aniline of formula (Y) by known methods, for example the Sandmeyer reaction, via the corresponding diazonium salts. Anilines of formula (Y) are known compounds, or may be made from known compounds, by known methods.

Additional compounds of formula (A) may be prepared by reacting a compound of formula (P), or a compound of formula (R) with an organolead reagent of formula (Z) under conditions described, for example, by J. Pinhey, Pure and Appl. Chem., (1996), 68 (4), 819 and by M. Moloney et al., Tetrahedron Lett., (2002), 43, 3407.

The organolead reagent of formula (Z) may be prepared from a boronic acid of formula (O), a stannane of formula (AA), wherein R is C₁-C₄ alkyl or by direct plumbation of a compound of formula (AB) with lead tetraacetate according to known procedures.

Further compounds of formula (A) may be prepared by reacting a compound of formula (P) or a compound of formula (R) with suitable triarylbismuth compound under conditions described, for example, by A. Yu. Fedorov et al., Russ. Chem. Bull. Int. Ed., (2005), 54 (11), 2602, and by P. Koech and M. Krische, J. Am. Chem. Soc., (2004), 126 (17), 5350 and references therein.

In a further approach, a compound of formula I may be prepared from a compound of formula (AC) by suitable derivatisation under standard conditions.

For example, compounds of formula (AC) are alkenes, and as such undergo further reactions typical of alkenes to give compounds of formula I according to known procedures. Examples of such reactions include, but are not restricted to, reduction, halogenation, epoxidation, cyclopropanation, dihydroxylation, hydroarylation, hydrovinylation and hydration. Compounds of formula (AC) wherein R⁸ or R⁹ is bromine or iodine are vinyl halides, and undergo known reactions of vinyl halides such as Suzuki-Miyaura, Sonogashira, Stille and related reactions. Certain other compounds of formula (AC), wherein R⁸ or R⁹ is C₁-C₆alkoxy, are enol ethers, and these may be hydrolysed to the corresponding ketone using standard procedures. In turn, the ketone produced may be further transformed, for example by ketalisation, oximation, reduction and the like under known conditions to give additional compounds of formula I. Similarly, compounds of formula (AC) wherein R⁸ or R⁹ is C₁-C₆amino or di-C₁-C₆amino are enamines, and these also may be hydrolysed to the corresponding ketone using standard procedures.

A compound of formula (AC), wherein G is C₁-C₄ alkyl, may be prepared from a compound of formula (AD), wherein G is C₁-C₄ alkyl and X is halogen or other suitable leaving group (such as an alkyl or arylsulfonate, or an arylselenoxide), by reaction with a compound of formula (I-1), optionally in a suitable solvent, and optionally in the presence of a suitable base.

Suitable solvents include toluene, dichloromethane and chloroform and suitable bases include organic bases such as triethylamine, Hunig's base and 1,8-diazabicyclo[5.4.0]undec-7-ene. Preferably the solvent is toluene and the base is 1,8-diazabicyclo[5.4.0]undec-7-ene.

A compound of formula (AD) may be prepared from a compound of formula (AE), under known conditions.

For example, a compound of formula (AD) wherein X is chlorine may be prepared by reacting a compound of formula (AE) with copper(II) chloride and lithium chloride according to the procedure of E. Kosower et al., J. Org. Chem., (1963), 28, 630.

Compounds of formula (AE) are known compounds or may be made from known compounds by known methods (see, for example, Y. Song, B. Kim and J- N Heo, Tetrahedron Lett., (2005), 46, 5977). Alternatively, a compound of formula (AE) wherein G is C₁-C₄alkyl may be prepared from a compound of formula (AE), wherein G is hydrogen, for example by reaction with a C₁₋₄ alkyl halide or a tri-C₁₋₄-alkylorthoformate. Compounds of formula (AE), wherein G is hydrogen, are known, or may be prepared from known compounds by known methods (see, for example, T. Wheeler, U.S. Pat. No. 4,338,122, U.S. Pat. No. 4,283,348, J. T. Kuethe et al., J. Org. Chem., (2002), 67, 5993, S. Buchwald et al., J. Am. Chem. Soc., (2003), 125, 11818).

Alternatively, a compound of formula (AE), wherein G is C₁₋₄alkyl, may be prepared by reacting a compound of formula (AF), wherein G is C₁₋₄alkyl and Z is a halogen, preferably bromine or iodine, with a boronic acid of formula (O) in the presence of a suitable metal catalyst, a suitable base, and optionally a suitable ligand, in a suitable solvent.

Suitable solvents include toluene and n-butanol, suitable bases include inorganic bases such as potassium phosphate, a suitable metal catalyst is a palladium catalyst, for example in the form of palladium(II)acetate, and suitable ligands include substituted phosphines, for example 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl.

Compounds of formula (AF) are known compounds, or may be prepared by methods known in the literature. For example a compound of formula (AF) wherein G is C₁₋₄alkyl and Z is a bromine atom may be prepared by reacting a compound of formula (AG), wherein G is C₁₋₄alkyl, with a suitable brominating agent, such as N-bromosuccinimide, in a suitable solvent, such as 1,2-dichloroethane, as described by R. Shepherd and A. White, J. Chem. Soc. Perkin Trans. 1 (1987), 10, 2153.

In a similar manner, a compound of formula (A) may be prepared from a compound of formula (AH) by suitable derivatisation under standard conditions.

For example, compounds of formula (AH) are alkenes, and as such undergo further reactions typical of alkenes to give compounds of formula (A) according to known procedures. Examples of such reactions include, but are not restricted to, reduction, halogenation, epoxidation, cyclopropanation, dihydroxylation, hydroarylation, hydrovinylation and hydration. Compounds of formula (AH) wherein R⁸ or R⁹ is bromine or iodine are vinyl halides, and undergo known reactions of vinyl halides such as Suzuki-Miyaura, Sonogashira, Stille and related reactions. Certain other compounds of formula (AH), wherein R⁸ or R⁹ is C₁-C₆alkoxy, are enol ethers, and these may be hydrolysed to the corresponding ketone using standard procedures. In turn, the ketone produced may be further transformed, for example by ketalisation, oximation, reduction and the like under known conditions to give additional compounds of formula (A). Similarly, compounds of formula (AH) wherein R⁸ or R⁹ is C₁-C₆amino or di-C₁-C₆amino are enamines, and these also may be hydrolysed to the corresponding ketone using standard procedures.

A compound of formula (AH) may be prepared from a compound of formula (AI) by reaction with a compound of formula (H), optionally in a suitable solvent, and optionally in the presence of a suitable catalyst. The compounds of formula (AI) have been particularly designed as intermediates in the synthesis of the compounds of the formula I.

Compounds of the formula (AI) having the specific formulae

are known under the CAS registry numbers 299968-82-4 and 528833-96-7, respectively.

Preferably the catalyst is a Lewis acid catalyst such as aluminium chloride, bismuth (III) chloride, bismuth (III) trifluoromethanesulfonate, boron trifluoride, cerium (III) chloride, copper (I) trifluoromethanesulfonate, diethylaluminium chloride, hafnium (IV) chloride, iron (III) chloride, lithium perchlorate, lithium trifluoromethanesulfonate, magnesium bromide, magnesium iodide, scandium (III) trifluoromethanesulfonate, tin (IV) chloride, titanium (IV) chloride, titanium (IV) isopropoxide, trimethyl aluminium, N-trimethylsilyl-bis(trifluoromethanesulfonyl)imide, trimethylsilyl trifluoromethane-sulfonate, ytterbium (III) trifluoromethanesulfonate, zinc iodide and zirconium (IV) chloride. Magnesium iodide is particularly preferred. Suitable solvents include those which are known to be effective solvents for conducting Diels-Alder reactions, among them, for example, chloroform, dichloromethane, diethyl ether, ethanol, methanol, perfluorinated alkanes, such as perfluorohexane, toluene, water, and ionic liquids such as 1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium hexafluorophosphate. Dichloromethane is particularly preferred as a solvent.

A compound of formula (AI), may be prepared by oxidising a compound of formula (AJ) in a suitable solvent such as toluene, acetone, chloroform, dichloromethane or 1,4-dioxane. A wide range of oxidants are suitable for effecting this transformation, including inorganic oxidants such as chromium trioxide, pyridinium dichromate, manganese dioxide and aluminium alkoxides such as aluminium isopropoxide, as well as organic oxidants such as 2,3-dichloro-5,6-dicyano-p-benzoquinone and hypervalent iodine oxidants such as 1,1,1,-tris(acetyloxy)-1,1-dihydro-1,2-benziodoxol-3-(1H)-one (Dess-Martin periodinane), Suitable procedures are described, for example, by K. Saito and H. Yamachika, U.S. Pat. No. 4,371,711. and by G. Piancatelli et al., Tetrahedron (1978), 34, 2775. The use of chromium trioxide in a mixture of sulfuric acid and acetone (Jones reagent) is preferred.

The compounds of the formula AI have been particularly designed as intermediates for the synthesis of the compounds of the formula I.

Particularly useful compounds of the formula AI are those, wherein R⁵ and R¹² are hydrogen.

In another group of useful compounds of the formula I, R¹, R² and R⁴ are independently of each other methyl or ethyl.

In another group of useful compounds of the formula I, R¹, R² and R⁴ are independently of each other methyl or ethyl, and R³, R⁵ and R¹² are hydrogen.

A compound of formula (AJ) may be prepared from a compound of formula (AK) by treatment with a suitable acid catalyst in the presence of water and optionally in the presence of a suitable solvent, according to known procedures.

For example, a compound of formula (AK) may be converted to a compound of formula (AJ) in the presence of an aqueous solution of an acid such as phosphoric acid or polyphosphoric acid as described, for example by K. Saito and H. Yamachika, U.S. Pat. No. 4,371,711. Alternatively a compound of formula (AJ) may be prepared from a compound of formula (AK) by rearrangement in the presence of a Lewis acid catalyst such as zinc chloride according to the procedure of G. Piancatelli et al., Tetrahedron, (1978), 34, 2775.

A compound of formula (AK) may be prepared by the reduction of a compound of formula (AL) by known conditions (see, for example R Silvestri et al., J. Med. Chem., 2005, 48, 4378-4388).

Compounds of formula (AL) are known, or may be made by known methods from known compounds (see, for example, L. Liebeskind et al., Org. Lett., (2003), 5 (17), 3033-3035, H. Firouzabadi, N. Iranpoor and F. Nowrouzi, Tetrahedron, (2004), 60,10843, R. Silvestri et al., J. Med. Chem., (2005), 48, 4378 and references therein).

Alternatively a compound of formula (AK) may be prepared by the addition of a suitable organometallic reagent such as an arylmagnesium halide of formula (AM) wherein Hal is a halide such as chloride, bromide or iodide, or an aryllithium reagent of formula (AN) or a diarylzinc reagent of formula (AO) to a furan-2-carboxaldehyde of formula (AP) according to known procedures (see, for example G. Panda et al., Tetrahedron Lett., (2005), 46, 3097).

Additional compounds of formula (AK) may be prepared from compounds of formula (AR) by reaction with a strong base, for a example an alkyl lithium reagent such as n-butyllithium, optionally in the presence of an additive such as tetramethylethylenediamine, and in a suitable solvent such as diethyl ether or tetrahydrofuran, followed by reaction with a benzaldehyde of formula (AS) as described, for example by I. Gupta and M. Ravikanth, J. Org. Chem., (2004), 69, 6796, A. M. Echavarren et al., J. Am. Chem. Soc., (2003), 125 (19), 5757, and by T. K. Chandrashekar et al., J. Org. Chem., (2002), 67, 6309-6319.

The organometallic reagents of formula (AM), formula (AN) and formula (AO) are known compounds or may be made by known methods from known compounds. Compounds of formula (AP), formula (AR) and formula (AS) are known compounds, or may be prepared from known compounds by known methods.

The compounds of formula I according to the invention can be used as herbicides in unmodified form, as obtained in the synthesis, but they are generally formulated into herbicidal compositions in a variety of ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, for example in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil flowables, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known, for example, from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. Such formulations can either be used directly or are diluted prior to use. Diluted formulations can be prepared, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

The formulations can be prepared, for example, by mixing the active ingredient with formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, for example finely divided solids, mineral oils, vegetable oils, modified vegetable oils, organic solvents, water, surface-active substances or combinations thereof. The active ingredients can also be contained in very fine microcapsules consisting of a polymer. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into their surroundings in controlled amounts (e.g. slow release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95% by weight of the capsule weight. The active ingredients can be present in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes comprise, for example, natural and synthetic gums, cellulose, styrene-butadiene copolymers, polyacrylonitrile, polyacrylate, polyester, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art in this connection. Alternatively it is possible for very fine microcapsules to be formed wherein the active ingredient is present in the form of finely divided particles in a solid matrix of a base substance, but in that case the microcapsule is not encapsulated.

The formulation adjuvants suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylenes carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG 400), propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and higher molecular weight alcohols, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like. Water is generally the carrier of choice for the dilution of the concentrates. Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montomorillonite, cottonseed husks, wheatmeal, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials, as described, for example, in CFR 180.1001. (c) & (d).

A large number of surface-active substances can advantageously be used both in solid and in liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they may be used as emulsifying, wetting or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters; and also further substances described e.g. in “McCutcheon's Detergents and Emulsifiers Annual”, MC Publishing Corp., Ridgewood, N.J., 1981.

Further adjuvants which can usually be used in pesticidal formulations include crystallisation inhibitors, viscosity-modifying substances, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing aids, anti-foams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion-inhibitors, fragrances, wetting agents, absorption improvers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, anti-freezes, microbiocides, and also liquid and solid fertilisers.

The formulations may also comprise additional active substances, for example further herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides.

The compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive used in the composition according to the invention is generally from 0.01 to 10%, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rhone-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as active components essentially 80% by weight alkyl esters of fish oils and 15% by weight methylated rapeseed oil, and also 5% by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of C₈-C₂₂ fatty acids, especially the methyl derivatives of C₁₂-C₁₈ fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being important. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.

The application and action of the oil additives can be further improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C₁₂-C₂₂ fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol types (Clariant AG). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants. The concentration of surface-active substances in relation to the total additive is generally from 1 to 30% by weight. Examples of oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Syngenta AG, CH) and Actipron® (BP Oil UK Limited, GB).

The said surface-active substances may also be used in the formulations alone, that is to say without oil additives.

Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture can contribute to a further enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation). The concentration of such solvents can be from 10 to 80% by weight of the total weight. Such oil additives, which may be in admixture with solvents, are described, for example, in U.S. Pat. No. 4,834,908. A commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation). Further oil additives that are preferred according to the invention are SCORE® (Syngenta Crop Protection Canada) and Adigor® (Syngenta Crop Protection Canada).

In addition to the oil additives listed above, in order to enhance the activity of the compositions according to the invention it is also possible for formulations of alkylpyrrolidones, (e.g. Agrimax®) to be added to the spray mixture. Formulations of synthetic latices, such as, for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. Bond®, Courier® or Emerald®) can also be used. Solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, can also be mixed into the spray mixture as activity-enhancing agents.

The herbicidal formulations generally contain from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of a compound of formula I and from 1 to 99.9% by weight of a formulation adjuvant, which preferably includes from 0 to 25% by weight of a surface-active substance. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The rate of application of the compounds of formula I may vary within wide limits and depends upon the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed or grass to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The compounds of formula I according to the invention are generally applied at a rate of 1-2000 g/ha, preferably 1-1000 g/ha and most preferably at 1-500 g/ha.

Preferred formulations have especially the following compositions:

(%=percent by weight):

Emulsifiable Concentrates:

active ingredient: 1 to 95%, preferably 60 to 90% surface-active agent: 1 to 30%, preferably 5 to 20% liquid carrier: 1 to 80%, preferably 1 to 35%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 5% solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surface-active agent: 1 to 40%, preferably 2 to 30%

Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80% surface-active agent: 0.5 to 20%, preferably 1 to 15% solid carrier: 5 to 95%, preferably 15 to 90%

Granules:

active ingredient: 0.1 to 30%, preferably 0.1 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%

The following Examples further illustrate, but do not limit, the invention.

F1. Emulsifiable concentrates a) b) c) d) active ingredient 5% 10% 25% 50% calcium dodecylbenzene- 6%  8%  6% 8% sulfonate castor oil polyglycol ether 4% —  4% 4% (36 mol of ethylene oxide) octylphenol polyglycol ether —  4% — 2% (7-8 mol of ethylene oxide) NMP — — 10% 20% arom. hydrocarbon 85%  78% 55% 16% mixture C₉-C₁₂

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

F2. Solutions a) b) c) d) active ingredient  5% 10% 50% 90% 1-methoxy-3-(3-methoxy- — 20% 20% — propoxy)-propane polyethylene glycol MW 400 20% 10% — — NMP — — 30% 10% arom. hydrocarbon 75% 60% — — mixture C₉-C₁₂

The solutions are suitable for application in the form of microdrops.

F3. Wettable powders a) b) c) d) active ingredient 5% 25%  50%  80% sodium lignosulfonate 4% — 3% — sodium lauryl sulfate 2% 3% —  4% sodium diisobutylnaphthalene- — 6% 5%  6% sulfonate octylphenol polyglycol ether — 1% 2% — (7-8 mol of ethylene oxide) highly disperse silicic acid 1% 3% 5% 10% kaolin 88%  62%  35%  —

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, yielding wettable powders which can be diluted with water to give suspensions of any desired concentration.

F4. Coated granules a) b) c) active ingredient 0.1% 5% 15% highly disperse silicic acid 0.9% 2% 2% inorg. carrier 99.0% 93% 83% (diameter 0.1-1 mm) e.g. CaCO₃ or SiO₂

The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is subsequently evaporated off in vacuo.

F5. Coated granules a) b) c) active ingredient 0.1% 5% 15% polyethylene glycol MW 200 1.0% 2% 3% highly disperse silicic acid 0.9% 1% 2% inorg. carrier 98.0% 92% 80% (diameter 0.1-1 mm) e.g. CaCO₃ or SiO₂

The finely ground active ingredient is applied uniformly, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

F6. Extruder granules a) b) c) d) active ingredient 0.1% 3% 5% 15% sodium lignosulfonate 1.5% 2% 3% 4% carboxymethylcellulose 1.4% 2% 2% 2% kaolin 97.0% 93% 90% 79%

The active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water. The resulting mixture is extruded and then dried in a stream of air.

F7. Dusts a) b) c) active ingredient 0.1% 1% 5% talcum 39.9% 49% 35% kaolin 60.0% 50% 60%

Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) c) d) active ingredient 3% 10%  25%  50%  ethylene glycol 5% 5% 5% 5% nonylphenol polyglycol ether — 1% 2% — (15 mol of ethylene oxide) sodium lignosulfonate 3% 3% 4% 5% carboxymethylcellulose 1% 1% 1% 1% 37% aqueous formaldehyde 0.2%   0.2%   0.2%   0.2%   solution silicone oil emulsion 0.8%   0.8%   0.8%   0.8%   water 87%  79%  62%  38% 

The finely ground active ingredient is intimately mixed with the adjuvants, yielding a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

The invention relates also to a method for the selective control of grasses and weeds in crops of useful plants, and for non-selective weed control, which comprises treating the useful plants or the area under cultivation or the locus thereof with a compound of formula I.

Crops of useful plants in which the compositions according to the invention can be used include especially cereals, in particular wheat and barley, rice, corn, rape, sugarbeet, sugarcane, soybean, cotton, sunflower, peanut and plantation crops.

The term “crops” is to be understood as also including crops that have been rendered tolerant to herbicides or classes of herbicides (for example ALS, GS, EPSPS, PPO and HPPD inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant e.g. to imidazolinones, such as imazamox, by conventional methods of breeding is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®. The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica. Control of monocotyledonous weeds, in particular Agrostis, Avena, Setaria, Lolium, Echinochloa, Bromus, Alopecurus and Sorghum is very extensive.

Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt-176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins and transgenic plants able to synthesise such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants that contain one or more genes which code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops and their seed material can be resistant to herbicides and at the same time also to insect feeding (“stacked” transgenic events). Seed can, for example, have the ability to express an insecticidally active Cry3 protein and at the same time be glyphosate-tolerant. The term “crops” is to be understood as also including crops obtained as a result of conventional methods of breeding or genetic engineering which contain so-called output traits (e.g. improved flavour, storage stability, nutritional content).

Areas under cultivation are to be understood as including land where the crop plants are already growing as well as land intended for the cultivation of those crop plants.

The compounds of formula I according to the invention can also be used in combination with further herbicides. Preferably, in these mixtures, the compound of the formula I is one of those compounds listed in Tables 1 to 146 below. The following mixtures of the compound of formula I are especially important:

compound of formula I+acetochlor, compound of formula I+acifluorfen, compound of formula I+acifluorfen-sodium, compound of formula I+aclonifen, compound of formula I+acrolein, compound of formula I+alachlor, compound of formula I+alloxydim, compound of formula I+allyl alcohol, compound of formula I+ametryn, compound of formula I+amicarbazone, compound of formula I+amidosulfuron, compound of formula I+aminopyralid, compound of formula I+amitrole, compound of formula I+ammonium sulfamate, compound of formula I+anilofos, compound of formula I+asulam, compound of formula I+atraton, compound of formula I+atrazine, compound of formula I+azimsulfuron, compound of formula I+BCPC, compound of formula I+beflubutamid, compound of formula I+benazolin, compound of formula I+benfluralin, compound of formula I+benfuresate, compound of formula I+bensulfuron, compound of formula I+bensulfuron-methyl, compound of formula I+bensulide, compound of formula I+bentazone, compound of formula I+benzfendizone, compound of formula I+benzobicyclon, compound of formula I+benzofenap, compound of formula I+bifenox, compound of formula I+bilanafos, compound of formula I+bispyribac, compound of formula I+bispyribac-sodium, compound of formula I+borax, compound of formula I+bromacil, compound of formula I+bromobutide, compound of formula I+bromoxynil, compound of formula I+butachlor, compound of formula I+butafenacil, compound of formula I+butamifos, compound of formula I+butralin, compound of formula I+butroxydim, compound of formula I+butylate, compound of formula I+cacodylic acid, compound of formula I+calcium chlorate, compound of formula I+cafenstrole, compound of formula I+carbetamide, compound of formula I+carfentrazone, compound of formula I+carfentrazone-ethyl, compound of formula I+CDEA, compound of formula I+CEPC; compound of formula I+chlorflurenol, compound of formula I+chlorflurenol-methyl, compound of formula I+chloridazon, compound of formula I+chlorimuron, compound of formula I+chlorimuron-ethyl, compound of formula I+chloroacetic acid, compound of formula I+chlorotoluron, compound of formula I+chlorpropham, compound of formula I+chlorsulfuron, compound of formula I+chlorthal, compound of formula I+chlorthal-dimethyl, compound of formula I+cinidon-ethyl, compound of formula I+cinmethylin, compound of formula I+cinosulfuron, compound of formula I+cisanilide, compound of formula I+clethodim, compound of formula I+clodinafop, compound of formula I+clodinafop-propargyl, compound of formula I+clomazone, compound of formula I+clomeprop, compound of formula I+clopyralid, compound of formula I+cloransulam, compound of formula I+cloransulam-methyl, compound of formula I+CMA, compound of formula I+4-CPB, compound of formula I+CPMF, compound of formula I+4-CPP, compound of formula I+CPPC, compound of formula I+cresol, compound of formula I+cumyluron, compound of formula I+cyanamide, compound of formula I+cyanazine, compound of formula I+cycloate, compound of formula I+cyclosulfamuron, compound of formula I+cycloxydim, compound of formula I+cyhalofop, compound of formula I+cyhalofop-butyl, compound of formula I+2,4-D, compound of formula I+3,4-DA, compound of formula I+daimuron, compound of formula I+dalapon, compound of formula I+dazomet, compound of formula I+2,4-DB, compound of formula I+3,4-DB, compound of formula I+2,4-DEB, compound of formula I+desmedipham, compound of formula I+dicamba, compound of formula I+dichlobenil, compound of formula I+ortho-dichlorobenzene, compound of formula I+para-dichlorobenzene, compound of formula I+dichlorprop, compound of formula I+dichlorprop-P, compound of formula I+diclofop, compound of formula I+diclofop-methyl, compound of formula I+diclosulam, compound of formula I+difenzoquat, compound of formula I+difenzoquat metilsulfate, compound of formula I+diflufenican, compound of formula I+diflufenzopyr, compound of formula I+dimefuron, compound of formula I+dimepiperate, compound of formula I+dimethachlor, compound of formula I+dimethametryn, compound of formula I+dimethenamid, compound of formula I+dimethenamid-P, compound of formula I+dimethipin, compound of formula I+dimethylarsinic acid, compound of formula I+dinitramine, compound of formula I+dinoterb, compound of formula I+diphenamid, compound of formula I+diquat, compound of formula I+diquat dibromide, compound of formula I+dithiopyr, compound of formula I+diuron, compound of formula I+DNOC, compound of formula I+3,4-DP, compound of formula I+DSMA, compound of formula I+EBEP, compound of formula I+endothal, compound of formula I+EPTC, compound of formula I+esprocarb, compound of formula I+ethalfluralin, compound of formula I+ethametsulfuron, compound of formula I+ethametsulfuron-methyl, compound of formula I+ethofumesate, compound of formula I+ethoxyfen, compound of formula I+ethoxysulfuron, compound of formula I+etobenzanid, compound of formula I+fenoxaprop-P, compound of formula I+fenoxaprop-P-ethyl, compound of formula I+fentrazamide, compound of formula I+ferrous sulfate, compound of formula I+flamprop-M, compound of formula I+flazasulfuron, compound of formula I+florasulam, compound of formula I+fluazifop, compound of formula I+fluazifop-butyl, compound of formula I+fluazifop-P, compound of formula I+fluazifop-P-butyl, compound of formula I+flucarbazone, compound of formula I+flucarbazone-sodium, compound of formula I+flucetosulfuron, compound of formula I+fluchloralin, compound of formula I+flufenacet, compound of formula I+flufenpyr, compound of formula I+flufenpyr-ethyl, compound of formula I+flumetsulam, compound of formula I+flumiclorac, compound of formula I+flumiclorac-pentyl, compound of formula I+flumioxazin, compound of formula I+fluometuron, compound of formula I+fluoroglycofen, compound of formula I+fluoroglycofen-ethyl, compound of formula I+flupropanate, compound of formula I+flupyrsulfuron, compound of formula I+flupyrsulfuron-methyl-sodium, compound of formula I+flurenol, compound of formula I+fluridone, compound of formula I+fluorochloridone, compound of formula I+fluoroxypyr, compound of formula I+flurtamone, compound of formula I+fluthiacet, compound of formula I+fluthiacet-methyl, compound of formula I+fomesafen, compound of formula I+foramsulfuron, compound of formula I+fosamine, compound of formula I+glufosinate, compound of formula I+glufosinate-ammonium, compound of formula I+glyphosate, compound of formula I+halosulfuron, compound of formula I+halosulfuron-methyl, compound of formula I+haloxyfop, compound of formula I+haloxyfop-P, compound of formula I+HC-252, compound of formula I+hexazinone, compound of formula I+imazamethabenz, compound of formula I+imazamethabenz-methyl, compound of formula I+imazamox, compound of formula I+imazapic, compound of formula I+imazapyr, compound of formula I+imazaquin, compound of formula I+imazethapyr, compound of formula I+imazosulfuron, compound of formula I+indanofan, compound of formula I+iodomethane, compound of formula I+iodosulfuron, compound of formula I+iodosulfuron-methyl-sodium, compound of formula I+ioxynil, compound of formula I+isoproturon, compound of formula I+isouron, compound of formula I+isoxaben, compound of formula I+isoxachlortole, compound of formula I+isoxaflutole, compound of formula I+karbutilate, compound of formula I+lactofen, compound of formula I+lenacil, compound of formula I+linuron, compound of formula I+MAA, compound of formula I+MAMA, compound of formula I+MCPA, compound of formula I+MCPA-thioethyl, compound of formula I+MCPB, compound of formula I+mecoprop, compound of formula I+mecoprop-P, compound of formula I+mefenacet, compound of formula I+mefluidide, compound of formula I+mesosulfuron, compound of formula I+mesosulfuron-methyl, compound of formula I+mesotrione, compound of formula I+metam, compound of formula I+metamifop, compound of formula I+metamitron, compound of formula I+metazachlor, compound of formula I+methabenzthiazuron, compound of formula I+methylarsonic acid, compound of formula I+methyldymron, compound of formula I+methyl isothiocyanate, compound of formula I+metobenzuron, compound of formula I+metolachlor, compound of formula I+S-metolachlor, compound of formula I+metosulam, compound of formula I+metoxuron, compound of formula I+metribuzin, compound of formula I+metsulfuron, compound of formula I+metsulfuron-methyl, compound of formula I+MK-616, compound of formula I+molinate, compound of formula I+monolinuron, compound of formula I+MSMA, compound of formula I+naproanilide, compound of formula I+napropamide, compound of formula I+naptalam, compound of formula I+neburon, compound of formula I+nicosulfuron, compound of formula I+nonanoic acid, compound of formula I+norflurazon, compound of formula I+oleic acid (fatty acids), compound of formula I+orbencarb, compound of formula I+orthosulfamuron, compound of formula I+oryzalin, compound of formula I+oxadiargyl, compound of formula I+oxadiazon, compound of formula I+oxasulfuron, compound of formula I+oxaziclomefone, compound of formula I+oxyfluorfen, compound of formula I+paraquat, compound of formula I+paraquat dichloride, compound of formula I+pebulate, compound of formula I+pendimethalin, compound of formula I+penoxsulam, compound of formula I+pentachlorophenol, compound of formula I+pentanochlor, compound of formula I+pentoxazone, compound of formula I+pethoxamid, compound of formula I+petrolium oils, compound of formula I+phenmedipham, compound of formula I+phenmedipham-ethyl, compound of formula I+picloram, compound of formula I+picolinafen, compound of formula I+pinoxaden, compound of formula I+piperophos, compound of formula I+potassium arsenite, compound of formula I+potassium azide, compound of formula I+pretilachlor, compound of formula I+primisulfuron, compound of formula I+primisulfuron-methyl, compound of formula I+prodiamine, compound of formula I+profluazol, compound of formula I+profoxydim, compound of formula I+prometon, compound of formula I+prometryn, compound of formula I+propachlor, compound of formula I+propanil, compound of formula I+propaquizafop, compound of formula I+propazine, compound of formula I+propham, compound of formula I+propisochlor, compound of formula I+propoxycarbazone, compound of formula I+propoxycarbazone-sodium, compound of formula I+propyzamide, compound of formula I+prosulfocarb, compound of formula I+prosulfuron, compound of formula I+pyraclonil, compound of formula I+pyraflufen, compound of formula I+pyraflufen-ethyl, compound of formula I+pyrazolynate, compound of formula I+pyrazosulfuron, compound of formula I+pyrazosulfuron-ethyl, compound of formula I+pyrazoxyfen, compound of formula I+pyribenzoxim, compound of formula I+pyributicarb, compound of formula I+pyridafol, compound of formula I+pyridate, compound of formula I+pyriftalid, compound of formula I+pyriminobac, compound of formula I+pyriminobac-methyl, compound of formula I+pyrimisulfan, compound of formula I+pyrithiobac, compound of formula I+pyrithiobac-sodium, compound of formula I+quinclorac, compound of formula I+quinmerac, compound of formula I+quinoclamine, compound of formula I+quizalofop, compound of formula I+quizalofop-P, compound of formula I+rimsulfuron, compound of formula I+sethoxydim, compound of formula I+siduron, compound of formula I+simazine, compound of formula I+simetryn, compound of formula I+SMA, compound of formula I+sodium arsenite, compound of formula I+sodium azide, compound of formula I+sodium chlorate, compound of formula I+sulcotrione, compound of formula I+sulfentrazone, compound of formula I+sulfometuron, compound of formula I+sulfometuron-methyl, compound of formula I+sulfosate, compound of formula I+sulfosulfuron, compound of formula I+sulfuric acid, compound of formula I+tar oils, compound of formula I+2,3,6-TBA, compound of formula I+TCA, compound of formula I+TCA-sodium, compound of formula I+tebuthiuron, compound of formula I+tepraloxydim, compound of formula I+terbacil, compound of formula I+terbumeton, compound of formula I+terbuthylazine, compound of formula I+terbutryn, compound of formula I+thenylchlor, compound of formula I+thiazopyr, compound of formula I+thifensulfuron, compound of formula I+thifensulfuron-methyl, compound of formula I+thiobencarb, compound of formula I+tiocarbazil, compound of formula I+topramezone, compound of formula I+tralkoxydim, compound of formula I+tri-allate, compound of formula I+triasulfuron, compound of formula I+triaziflam, compound of formula I+tribenuron, compound of formula I+tribenuron-methyl, compound of formula I+tricamba, compound of formula I+triclopyr, compound of formula I+trietazine, compound of formula I+trifloxysulfuron, compound of formula I+trifloxysulfuron-sodium, compound of formula I+trifluralin, compound of formula I+triflusulfuron, compound of formula I+triflusulfuron-methyl, compound of formula I+trihydroxytriazine, compound of formula I+tritosulfuron, compound of formula I+[3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS RN 353292-31-6), compound of formula I+4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo)-1H-1,2,4-triazol-1-ylcarbonylsulfamoyl]-5-methylthiophene-3-carboxylic acid (BAY636), compound of formula I+BAY747 (CAS RN 335104-84-2), compound of formula I+topramezone (CAS RN 210631-68-8), compound of formula I+4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one (CAS RN 352010-68-5), and compound of formula I+4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one.

The mixing partners for the compound of formula I may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 12th Edition (BCPC) 2000.

The compounds of formula I according to the invention can also be used in combination with safeners. Preferably, in these mixtures, the compound of the formula I is one of those compounds listed in Tables 1 to 146 below. The following mixtures with safeners, especially, come into consideration:

compound of formula I+cloquintocet-mexyl, compound of formula I+cloquintocet acid and salts thereof, compound of formula I+fenchlorazole-ethyl, compound of formula I+fenchlorazole acid and salts thereof, compound of formula I+mefenpyr-diethyl, compound of formula I+mefenpyr diacid, compound of formula I+isoxadifen-ethyl, compound of formula I+isoxadifen acid, compound of formula I+furilazole, compound of formula I+furilazole R isomer, compound of formula (I)+N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide, compound of formula I+benoxacor, compound of formula I+dichlormid, compound of formula I+AD-67, compound of formula I+oxabetrinil, compound of formula I+cyometrinil, compound of formula I+cyometrinil Z-isomer, compound of formula I+fenclorim, compound of formula I+cyprosulfamide, compound of formula I+naphthalic anhydride, compound of formula I+flurazole, compound of formula I+CL 304,415, compound of formula I+dicyclonon, compound of formula I+fluxofenim, compound of formula I+DKA-24, compound of formula I+R-29148 and compound of formula I+PPG-1292. A safening effect can also be observed for the mixtures compound of the formula I+dymron, compound of the formula I+MCPA, compound of the formula I+mecopropand compound of the formula I+mecoprop-P.

The above-mentioned safeners and herbicides are described, for example, in the Pesticide Manual, Twelfth Edition, British Crop Protection Council, 2000. R-29148 is described, for example by P. B. Goldsbrough et al., Plant Physiology, (2002), Vol. 130 pp. 1497-1505 and references therein, PPG-1292 is known from WO09211761 and N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide is known from EP365484.

Benoxacor, cloquintocet-mexyl, cyprosulfamide, mefenpyr-diethyl and N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide are especially preferred, where cloquintocet-mexyl is particularly valuable.

It is preferred to apply the other herbicide together with one of the safeners mentioned above.

The following Examples illustrate the invention further but do not limit the invention.

PREPARATION EXAMPLES

Those skilled in the art will appreciate that certain compounds described below are β-ketoenols, and as such may exist as a single tautomer or as a mixture of keto-enol and diketone tautomers, as described, for example by J. March, Advanced Organic Chemistry, third edition, John Wiley and Sons. The compounds shown below, and in Table T1 are drawn as an arbitrary single enol tautomer, but it should be inferred that this description covers both the diketone form and any possible enols which could arise through tautomerism. Where more than one tautomer is observed in proton NMR, the data shown are for the mixture of tautomers. Furthermore, some of the compounds shown below are drawn as single enantiomers for the purposes of simplicity, but unless specified as single enantiomers, these structures should be construed as representing a mixture of enantiomers. Additionally, some of the compounds can exist as diastereoisomers, and it should be inferred that these can be present as a mixture of diastereoisomers or as any possible single diastereoisomer. Within the detailed experimental section the diketone tautomer is chosen for naming purposes, even if the predominant tautomer is the enol form.

Example 1 Preparation of (1RS,2SR,6RS,7SR)-4-(2,6-diethyl-4-methylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione

Step 1: Preparation of (1RS,2SR,6RS,7SR)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-ene-3,5-dione

Furan (13.9 ml, 0.19 mol) is added to cyclopentene-1,4-dione (18.4 g, 0.19 mol) and the reaction mixture is stirred at room temperature for 5 days. The mixture is diluted with methanol and (1RS,2SR,6RS,7SR)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-ene-3,5-dione is collected by filtration, and used without further purification in the next step.

Step 2: Preparation of (1RS,2SR,6RS,7SR)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione

(1RS,2SR,6RS,7SR)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-ene-3,5-dione (2.1 g, 12.8 mmol), prepared in Step 1, is dissolved in warm methanol (180 ml) and the mixture is allowed to cool to room temperature. The mixture is then hydrogenated in the presence of 5% palladium on carbon (approx. 50 mg) at 3.5 bar for 4 hours. The catalyst is removed by filtration through diatomaceous earth and the filtrate is concentrated under reduced pressure to afford (1RS,2SR,6RS,7SR)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione.

Step 3: Preparation of (1RS,2SR,6RS,7SR)-4-(2,6-diethyl-4-methylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione

Iodobenzene diacetate (10.3 g, 32.0 mol) and sodium carbonate (3.38 g, 32.0 mmol) are suspended in water (100 ml) and the resultant yellow suspension is stirred at room temperature for 30 minutes. Meanwhile, (1RS,2SR,6RS,7SR)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione (5.3 g, 32.0 mol) is added to a solution of sodium carbonate (3.38 g, 32.0 mol) in water (50 ml) and ethanol (50 ml) and the mixture is stirred at room temperature to produce an orange solution. The two mixtures are combined and stirred for 3 hours at room temperature, then the mixture is poured into water and extracted with dichloromethane. The organic extracts are combined, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated under reduced pressure to give an iodonium ylide, used without further purification in the next step.

The iodonium ylide (3 g, 8.15 mmol), prepared above, is added to a solution of 2,6-diethyl-4-methylphenylboronic acid (1.57 g, 8.15 mmol), tetrabutylammonium bromide (2.63 g, 8.15 mmol), lithium hydroxide monohydrate (1.03 g, 24.5 mmol) and palladium (II)acetate (92 mg, 0.41 mmol) in 1,2-dimethoxyethane (80 ml) and water (20 ml) and the reaction mixture is heated at 50° C. for 5 hours under an atmosphere of nitrogen. The reaction mixture is cooled to room temperature and partitioned between dilute aqueous hydrochloric acid and ethyl acetate. The organic phase is then extracted into 0.5 M aqueous potassium carbonate solution and the organic phase discarded. The aqueous phase is acidified with concentrated hydrochloric acid and extracted with ethyl acetate. The organic extract is dried over anhydrous magnesium sulfate, filtered and the filtrate concentrated under reduced pressure. The residue is purified by column chromatography on silica gel to afford (1RS,2SR,6RS,7SR)-4-(2,6-diethyl-4-methylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione.

¹H NMR (400 MHz, CDCl₃) δ_(H) 6.88-6.87 (2H, m), 4.55-4.54 (2H, m), 2.62 (2H, s), 2.36-2.27 (7H, m), 1.69-1.67 (2H, m), 1.40-1.39 (2H, m), 1.03 (6H, q).

Example 2 Preparation of (1RS, 2RS,6SR,7SR)-4-(2,6-diethyl-4-methylphenyl)-5-methoxy-10-oxa-tricyclo[5.2.1.0^(2,6)]deca-4,8-dien-3-one

Step 1: Preparation of 2-bromo-3-methoxycyclopent-2-enone

N-Bromosuccinimide (24.92 g, 0.140 mol) is added, portionwise, over 1 hour to a stirred solution of 3-methoxycyclopent-2-enone (14.95 g, 0.133 mol) in 1,2-dichloroethane (300 ml) at 0° C. in an amber flask. The reaction mixture is stirred at 0° C. for a further 90 minutes and then any remaining solid is removed by filtration. The filtrate is evaporated to dryness under reduced pressure, the resultant solid is dissolved in warm toluene (600 ml) and washed quickly with ice-cold water (2×100 ml). The organic phase is dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated under reduced pressure until approximately 150 ml remains. The residue is cooled with an ice bath and left for 30 minutes. The resultant solid is removed by filtration, washed with hexane (50 ml) and air-dried to give 2-bromo-3-methoxycyclopent-2-enone.

Step 2: Preparation of 2-(2,6-diethyl-4-methylphenyl)-3-methoxycyclopent-2-enone

To a stirred suspension of 2-bromo-3-methoxycyclopent-2-enone (17.5 g, 91.6 mmol), 2,6-diethyl-4-methylphenyl boronic acid (26.4 g, 137 mmol) and freshly powdered potassium phosphate (38.9 g, 183 mmol) in anhydrous, degassed toluene (450 ml) under a nitrogen atmosphere are added palladium (II)acetate (0.411 g, 1.83 mmol) and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (1.51 g, 3.67 mmol). The reaction mixture is heated at 90° C. for 6.5 hours and then allowed to cool to room temperature overnight. The reaction is diluted with water (400 ml) and extracted with ethyl acetate (3×150 ml). The combined organic extracts are washed with brine (50 ml), dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated to dryness under reduced pressure to give a brown oil. The crude product is purified by column chromatography on silica gel to give 2-(2,6-diethyl-4-methylphenyl)-3-methoxycyclopent-2-enone.

Step 3: Preparation of 5-chloro-2-(2,6-diethyl-4-methylphenyl)-3-methoxycyclopent-2-enone

To a stirred solution of 2-(2,6-diethyl-4-methylphenyl)-3-methoxycyclopent-2-enone (0.715 g, 2.77 mmol) in 1,4-dioxane (45 ml), and under an atmosphere of nitrogen, are added copper (II) chloride (0.743 g, 5.53 mmol) and lithium chloride (0.176 g, 4.15 mmol). The reaction is heated at reflux for 7 hours and allowed to cool to room temperature overnight. The remaining solid is removed by filtration and washed with ethyl acetate (50 ml). The filtrate is washed with water (2×25 ml) and the aqueous washings re-extracted with ethyl acetate (1.5 ml). The combined organic phases are washed with brine (15 ml), dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure to give a brown oil. The crude product is purified by column chromatography on silica gel to give 5-chloro-2-(2,6-diethyl-4-methylphenyl)-3-methoxycyclopent-2-enone.

Step 4: Preparation of (1RS,2RS,6SR,7SR)-4-(2,6-diethyl-4-methylphenyl)-5-methoxy-10-oxa-tricyclo[5.2.1.0^(2,6)]deca-4,8-dien-3-one

To a stirred solution of 5-chloro-2-(2,6-diethyl-4-methylphenyl)-3-methoxycyclopent-2-enone (0.530 g, 1.81 mmol) in furan (40 ml) at room temperature is added by syringe pump over two hours a solution of 1,8-diazabicyclo[5.4.0]undec-7-ene (0.540 ml, 3.62 mmol) in furan (10 ml). The reaction is stirred at room temperature for a further 30 minutes and then evaporated to dryness under reduced pressure. The residue is diluted with water (50 ml), 2 M aqueous hydrochloric acid (25 ml) is added and the mixture is extracted with ethyl acetate (3×50 ml). The combined organic extracts are washed with brine (20 ml), dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated to dryness under reduced pressure. The residue is purified by column chromatography on silica gel to give (1RS,2RS,6SR,7SR)-4-(2,6-diethyl-4-methylphenyl)-5-methoxy-10-oxa-tricyclo[5.2.1.0^(2,6)]deca-4,8-dien-3-one.

¹H NMR (400 MHz, CDCl₃) δ_(H) 6.90 (2H, s), 6.45 (1H, dd), 6.35 (1H, dd), 5.30 (1H, d), 5.25 (1H, d), 3.65 (3H, s), 3.65 (1H, dd), 3.45 (1H, dd), 2.35 (4H, m), 2.30 (3H, s), 1.10 (6H, m).

Note: A quantity of (1RS,2SR,6RS,7SR)-4-(2,6-diethyl-4-methylphenyl)-5-methoxy-10-oxatricyclo[5.2.1.0^(2,6)]deca-4,8-dien-3-one is also formed during the course of this reaction.

Example 3 Preparation of (1RS,2RS,6SS,7SR)-4-(2,6-diethyl-4-methylphenyl)-5-methoxy-10-oxa-tricyclo[5.2.1.0^(2,6)]dec-4-en-3-one

To a solution of (1RS,2RS,6SR,7SR)-4-(2,6-diethyl-4-methylphenyl)-5-methoxy-10-oxa-tricyclo[5.2.1.0^(2,6)]deca-4,8-dien-3-one (0.052 g, 0.16 mmol) in methanol (10 ml) is added 5% palladium on carbon (10 mg). The reaction is stirred under an atmosphere of hydrogen for 90 minutes. The reaction is filtered through diatomaceous earth and the filter pad is washed with ethyl acetate (10 ml). The solvent is removed under reduced pressure to yield (1RS,2RS,6-SR,7SR)-4-(2,6-diethyl-4-methylphenyl)-5-methoxy-10-oxa-tricyclo[5.2.1.0^(2,6)]dec-4-en-3-one.

¹H NMR (400 MHz, CDCl₃) δ_(H) 6.90 (2H, m), 4.85 (2H, m), 3.70 (3H, s), 3.60 (1H, m), 3.35 (1H, dd), 2.50 (2H, m), 2.35 (2H, m), 2.30 (3H, s), 1.90-1.75 (4H, m), 1.20 (3H, t), 1.10 (3H, t).

Example 4 Preparation of (1RS,2RS,6SS,7SR)-4-(2,6-diethyl-4-methylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione

To a solution of (1RS,2RS,6SR,7SR)-4-(2,6-diethyl-4-methylphenyl)-5-methoxy-10-oxa-tricyclo[5.2.1.0^(2,6)]dec-4-en-3-one (0.049 g, 0.15 mmol) in THF (1 ml) in a 5 ml microwave vial is added 2 M aqueous hydrochloric acid (4 ml). The reaction mixture is at 140° C. under microwave irradiation for 50 minutes. The reaction mixture is cooled to room temperature, diluted with 2 M aqueous potassium carbonate solution (20 ml) and washed with diethyl ether (2×5 ml). The pH of the aqueous phase is adjusted to approx. 2 by addition of 5 M aqueous hydrochloric acid and then extracted with ethyl acetate (3×10 ml). The combined organic extracts are washed with brine (10 ml), dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated to dryness under reduced pressure to give a yellow oil. The crude product is purified by column chromatography on silica gel to give (1RS,2RS,6SS,7SR)-4-(2,6-diethyl-4-methylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione.

¹H NMR (400 MHz, CDCl₃) δ_(H) 6.95 (2H, s), 4.75 (2H, br), 3.40 (2H, br), 2.45 (2H, q), 2.35 (2H, q), 2.30 (3H, s), 1.80 (4H, m), 1.15 (3H, t), 1.05 (3H, t).

Example 5 Preparation of (1RS,2SR,6RS,7SR)-4-(2,6-diethyl-4-methylphenyl)-5-methoxy-10-oxatricyclo[5.2.1.0^(2,6)]dec-4-en-3-one

Step 1: Preparation of (1RS,2SR,6RS,7SR)-5-methoxy-10-oxatricyclo[5.2.1.0^(2,6)]dec-4-en-3-one

Iodine (0.10 g, 0.38 mmol) is added to a solution of (1RS,2SR,6RS,7SR)-10-oxa-tricyclo[5.2.1.0^(2,6)]decane-3,5-dione (2.1 g, 12.65 mmol) in methanol (50 ml) and the reaction mixture is stirred for 2 hours at room temperature. The solvent is then removed under reduced pressure, dichloromethane is added and the organic layer is washed with saturated aqueous sodium thiosulfate solution, water and brine. The organic layer is dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure to give (1RS,2SR,6RS,7SR)-5-methoxy-10-oxatricyclo[5.2.1.0^(2,6)]dec-4-en-3-one and used without further purification in the next step.

Step 2: Preparation of (1RS,2SR,6RS,7SR)-4-bromo-5-methoxy-10-oxatricyclo[5.2.1.0^(2,6)]dec-4-en-3-one

A solution of bromine (0.14 ml, 2.8 mmol) in dichloromethane (5 ml) is added dropwise to a solution of the enol ether (0.48 g, 2.6 mmol) prepared in step 1 in dichloromethane (40 ml) at 0° C. and the reaction mixture is stirred for 1 hour. Triethylamine (0.64 ml, 4.6 mmol) is then added and the reaction mixture is allowed to warm to room temperature and then stirred for 3 hours. The reaction mixture is washed with 2M aqueous hydrochloric acid and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated under reduced pressure. The residue is purified by column chromatography on silica gel to give (1RS,2SR,6RS,7SR)-4-bromo-5-methoxy-10-oxatricyclo[5.2.1.0^(2,6)]dec-4-en-3-one.

Step 3: Preparation of (1RS,2SR,6RS,7SR)-4-(2,6-diethyl-4-methylphenyl)-5-methoxy-10-oxatricyclo[5.2.1.0^(2,6)]dec-4-en-3-one

A mixture of (1RS, 2SR,6RS,7SR)-4-bromo-5-methoxy-10-oxatricyclo[5.2.1.0^(2,6)]dec-4-en-3-one (0.315 g, 1.2 mmol), 2,6-diethyl-4-methylphenylboronic acid (0.35 g, 1.8 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (20 mg, 0.048 mmol), palladium (II)acetate (5.5 mg, 0.024 mmol) and potassium phosphate (0.51 g, 2.4 mmol) are heated in degassed toluene at 95° C. for 24 hours. The reaction mixture is partitioned between dichloromethane and water, and the organic phase is dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure. The residue is purified by column chromatography on silica gel to give (1RS,2SR,6RS,7SR)-4-(2,6-diethyl-4-methylphenyl)-5-methoxy-10-oxatricyclo[5.2.1.0^(2,6)]dec-4-en-3-one.

¹H NMR (400 MHz, CDCl₃) δ_(H) 6.90 (1H, s), 6.80 (1H, s), 4.73 (1H, d), 4.66 (1H, d), 3.58 (3H, s), 2.91 (1H, d), 2.66 (1H, d), 2.50-2.36 (4H, m), 2.30 (3H, s), 1.88-1.81 (2H, m), 1.62-1.56 (2H, m), 1.12-1.09 (6H, m).

Example 6 Preparation of (1RS,2SR,6RS,7SR)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione

Step 1: Preparation of (2,4,6-trimethylphenyl)furan-2-ylmethanol

A solution of 2,4,6-trimethyl-1-bromobenzene (30.9 g, 155 mmol) in tetrahydrofuran (100 ml) is added slowly to magnesium turnings (3.77 g, 155 mmol), until the magnesium is just covered. A small quantity of iodine is added and the mixture is allowed to stand at room temperature for 25 minutes and then heated and stirred until the brown colour is lost. The remainder of the aryl bromide solution is added dropwise over a 20 minute period, with occasional heating to maintain the formation of the Grignard reagent solution. The reaction is stirred at room temperature for 1 hour. A solution of furfural (12.8 ml, 155 mmol) in tetrahydrofuran (70 ml) is added dropwise, and once the addition is complete, the reaction is stirred at room temperature for 2 hours. The reaction is quenched by cautious addition of excess saturated ammonium chloride solution, then extracted into ethyl acetate, washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Purification by column chromatography on silica gel affords (2,4,6-trimethylphenyl)furan-2-ylmethanol.

Step 2: Preparation of 5-(2,4,6-trimethylphenyl)-4-hydroxycyclopent-2-enone

A solution of (2,4,6-trimethylphenyl)furan-2-ylmethanol (27.8 g, 129 mmol) in acetone (730 ml) and water (100 ml) is heated to 55° C. and polyphosphoric acid (2 g) is added. The mixture is stirred at 55° C. for 7 hours, then cooled to room temperature overnight. The reaction mixture is concentrated under reduced pressure to remove most of the acetone then ethyl acetate (500 ml) is added, and the reaction mixture is partitioned. The aqueous phase is extracted into ethyl acetate and the organic solutions are combined, washed with saturated aqueous sodium bicarbonate solution and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure. The residue is purified by column chromatography on silica gel to give 5-(2,4,6-trimethylphenyl)-4-hydroxycyclopent-2-enone.

Step 3: Preparation of 2-(2,4,6-trimethylphenyl)cyclopent-4-ene-1,3-dione

Jones' reagent (138 ml of 1.67 M solution, 230 mmol) is added dropwise over 40 minutes to a cooled (ice-bath) solution of 5-(2,4,6-trimethylphenyl)-4-hydroxycyclopent-2-enone (49.66 g, 230 mmol) in acetone (600 ml). The mixture is stirred for 1 hour. Isopropanol (100 ml) is added and the mixture is stirred at room temperature for 2 hours. The mixture is diluted with ethyl acetate and washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure to give 2-(2,4,6-trimethylphenyl)cyclopent-4-ene-1,3-dione.

Step 4: Preparation of (1RS,2SR,6RS,7SR)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]dec-8-en-3,5-dione

Furan (214 ml, 3.15 mol) and magnesium iodide (7.0 g, 0.025 mol) are added to 2-(2,4,6-trimethylphenyl)cyclopent-4-ene-1,3-dione (27.0 g, 0.126 mol) and the mixture is stirred at room temperature for 4 days. The reaction mixture is concentrated under reduced pressure and the residue is purified by column chromatography on silica gel to give (1RS,2SR,6RS,7SR)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione.

¹H NMR (400 MHz, CDCl₃) δ_(H) 6.86 (2H, s), 6.47 (2H, s), 5.01 (2H, s), 2.74 (2H, s), 2.23 (3H, s), 2.08 (3H, s), 2.06 (3H, s).

Example 7 Preparation of (1RS,2SR,6RS,7SR)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione

A solution of (1RS,2SR,6RS,7SR)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione (205 mg, 0.66 mmol) in methanol (250 ml) is hydrogenated at 2 bar over 5% palladium on carbon (approximately 20 mgs) for 1 hour at room temperature. The catalyst is removed by filtration through diatomaceous earth and the solvent is evaporated under reduced pressure. Trituration with diethyl ether gives (1RS,2SR,6RS,7SR)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione.

¹H NMR (400 MHz, d₄-MeOH) δ_(H) 6.88 (2H, s), 4.61 (2H, s), 2.87 (2H, s), 2.27 (3H, s), 2.06 (6H, s), 1.84-1.82 (2H, m), 1.71-1.66 (2H, m).

Example 8 Preparation of (1RS,2SR,6RS,7RS)-4-(2,4,6-trimethylphenyl)-8-trimethylsilylethynyl-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione

3-(Trimethylsilylethynyl)furan (10.0 g, 61 mmol) and magnesium iodide (1.11 g, 4 mmol) are added to 2-(2,4,6-trimethylphenyl)cyclopent-4-ene-1,3-dione (4.34 g, 20 mmol) and the mixture is stirred at room temperature for 3 days. The reaction mixture is concentrated under reduced pressure and the residue is purified by column chromatography on silica gel to give (1RS,2SR,6RS,7RS)-4-(2,4,6-trimethylphenyl)-8-trimethylsilylethynyl-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione.

¹H NMR (400 MHz, CDCl₃) δ_(H) 6.65 (2H, s), 6.26 (1H, s), 4.75 (1H, s), 4.67 (1H, s), 2.62 (1H, d), 2.52 (1H, d), 2.03 (3H, s), 1.84 (3H, s), 1.80 (3H, s), 0.00 (9H, s).

Example 9 Preparation of (1RS,2SR,6RS,7RS)-8-ethynyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione

Potassium carbonate (2.58 g, 19 mmol) is added to a stirred solution of (1RS,2SR,6RS,7RS)-4-(2,4,6-trimethylphenyl)-8-trimethylsilylethynyl-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione (6.43 g, 17 mmol) in methanol (100 ml). The reaction mixture is stirred at room temperature for 2 hours and 30 minutes, then dilute aqueous hydrochloric acid is added and the mixture is extracted with ethyl acetate. The organic extracts are combined, dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure to give (1RS,2SR,6RS,7RS)-8-ethynyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione.

¹H NMR (400 MHz, d₄-MeOH) δ_(H) 6.85 (2H, s), 6.72 (1H, d), 5.03 (1H, d), 3.96 (1H, s), 2.92-2.88 (2H, m), 2.24 (3H, s), 2.06 (3H, s), 2.01 (3H, s).

Example 10 Preparation of (1RS,2SR,6RS,7SR,8RS)-8-ethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione and (1RS,2SR,6RS,7SR,8SR)-8-ethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione

A solution of (1RS,2SR,6RS,7RS)-8-ethynyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione (1.0 g, 3.3 mmol) in methanol (100 ml) and dichloromethane (100 ml) is hydrogenated at 3.5 bar over 5% palladium on carbon (approximately 50 mg) until the reaction is judged to be complete by mass spectrometry. The catalyst is removed by filtration through diatomaceous earth and the solvent is evaporated under reduced pressure. Purification by column chromatography on silica gel gives an approximately 1:1 mixture of (1RS,2SR,6RS,7SR,8RS)-8-ethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione and (1RS,2SR,6RS,7SR,8SR)-8-ethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione.

(1RS,2SR,6RS,7SR,8RS)-8-ethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione: ¹H NMR (400 MHz, CDCl₃) δ_(H) 6.82 (2H, s), 4.44 (1H, d), 4.24 (1H, s), 2.45-2.40 (2H, m), 2.22 (3H, s), 2.02 (6H, s), 1.58-1.52 (2H, m), 1.38-1.33 (1H, m), 1.25-1.16 (2H, m), 0.85-0.82 (3H, m).

(1RS,2SR,6RS,7SR,8SR)-8-ethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione: ¹H NMR (400 MHz, CDCl₃) δ_(H) 6.85 (2H, s), 4.51 (1H, d), 4.43 (1H, d), 3.07 (1H, d), 2.82-2.81 (1H, m), 2.24 (3H, s), 2.10-2.05 (2H, m), 2.04 (6H, s), 1.87-1.79 (1H, m), 1.53-1.46 (2H, m), 1.00 (3H, t).

Example 11 Preparation of (1RS,2SR,6RS,7SR)-4-(5-bromo-2-ethylphenyl)-1,7-dimethyl-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione

Step 1: Preparation of (5-bromo-2-ethylphenyl)furan-2-ylmethanol

4-Bromo-2-iodoethyl benzene (50.0 g, 0.161 mol) is dissolved in anhydrous tetrahydrofuran (250 ml) and cooled to −70° C. under an atmosphere of nitrogen. Isopropylmagnesium chloride (2 M solution in THF, 100 ml, 0.200 mmol) is added dropwise with vigorous stirring over 40 minutes, maintaining the internal temp below −60° C. by external cooling. When the addition is complete, the reaction is stirred at −70° C. for 20 minutes then allowed to warm to room temperature over 1 hour and 20 minutes. The reaction mixture is then cooled to −70° C. and a solution of 2-furaldehyde (16 ml, 18.6 g, 190 mmol) in tetrahydrofuran (50 ml) is added dropwise over 40 minutes. On completion of the addition, the reaction is allowed to warm to room temperature and stirred at room temperature for 3 hours. Saturated aqueous ammonium chloride solution (˜500 ml) is added and the mixture is extracted into ethyl acetate. The organic solutions are combined, washed with brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue is further purified by column chromatography on silica gel to give (5-bromo-2-ethylphenyl)-furan-2-ylmethanol.

Step 2: Preparation of 5-(5-bromo-2-ethylphenyl)-4-hydroxycyclopent-2-enone

A solution of (5-bromo-2-ethylphenyl)furan-2-ylmethanol (40.73 g, 0.145 mol) in acetone (1150 ml) and water (170 ml) is heated to 55° C. and 30 drops of polyphosphoric acid are added. The mixture is stirred at 55° C. for 44 hours, then cooled to room temperature. The reaction mixture is concentrated under reduced pressure to remove most of the acetone then ethyl acetate (500 ml) is added, and the reaction mixture is partitioned. The aqueous phase is extracted into ethyl acetate and the organic solutions are combined, washed with saturated aqueous sodium bicarbonate solution and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure. The residue is purified by column chromatography on silica gel to give 5-(5-bromo-2-ethylphenyl)-4-hydroxycyclopent-2-enone.

Step 3: Preparation of 2-(5-bromo-2-ethylphenyl)cyclopent-4-ene-1,3-dione

Jones' reagent (75 ml of 1.67 M solution, 125 mmol) is added dropwise over 30 minutes to a cooled (ice-bath) solution of 5-(5-bromo-4-ethylphenyl)-4-hydroxycyclopent-2-enone (33 g, 117 mmol) in acetone (400 ml). The mixture is stirred for 20 minutes, then the cooling bath is removed and the mixture is stirred for 1 hour at room temperature. Isopropanol (150 ml) is added to the yellow slurry and the mixture is stirred at room temperature for 2 hours. The mixture is diluted with ethyl acetate and washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure to give 2-(5-bromo-2-ethylphenyl)cyclopent-4-ene-1,3-dione.

Step 4: Preparation of (1RS,2SR,6RS,7SR)-4-(5-bromo-2-ethylphenyl)-1,7-dimethyl-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione

2,5-Dimethylfuran (2.3 ml, 21.6 mmol) and magnesium iodide (0.40 g, 1.4 mmol) are added to a solution of 2-(5-bromo-2-ethylphenyl)cyclopent-4-ene-1,3-dione (2.0 g, 7.2 mmol) in dichloromethane (10 ml) and the mixture is stirred at room temperature for 3 days. The reaction mixture is concentrated under reduced pressure and the residue is purified by column chromatography on silica gel to give (1RS,2SR,6RS,7SR)-4-(5-bromo-2-ethylphenyl)-1,7-dimethyl-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione.

¹H NMR (400 MHz, d₄-MeOH) δ_(H) 7.39 (1H, dd), 7.18 (1H, d), 7.16 (1H, d), 6.35 (2H, s), 2.79 (2H, s), 2.46 (2H, q), 1.61 (6H, s), 1.07 (3H, t).

Example 12 Preparation of (1RS,2SR,6RS,7SR)-4-(5-bromo-2-ethylphenyl)-1,7-dimethyl-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione

A solution of (1RS,2SR,6RS,7SR)-4-(5-bromo-2-ethylphenyl)-1,7-dimethyl-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione (1.63 g, 4.3 mmol) in methanol (200 ml) is hydrogenated at 3.5 bar over 5% palladium on carbon for 1 hour and 30 minutes at room temperature. The catalyst is removed by filtration through diatomaceous earth and the solvent is evaporated under reduced pressure. Trituration with diethyl ether gives (1RS,2SR,6RS,7SR)-4-(5-bromo-2-ethylphenyl)-1,7-dimethyl-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione.

¹H NMR (400 MHz, d₄-MeOH) δ_(H) 7.36 (1H, dd), 7.17 (1H, d), 7.15 (1H, d), 2.81 (2H, s), 2.48-2.43 (2H, m), 1.84-1.79 (2H, m), 1.69-1.65 (2H, m), 1.51 (6H, s), 1.08 (3H, t).

Example 13 Preparation of (1RS,2SR,6RS,7SR)-4-(5-bromo-2-ethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione

Furan (4.0 ml, 55.0 mmol) and magnesium iodide (1.00 g, 3.6 mmol) are added to a solution of 2-(5-bromo-2-ethylphenyl)cyclopent-4-ene-1,3-dione (5.0 g, 17.9 mmol) in dichloromethane (20 ml) and the mixture is stirred at room temperature for 3 days. A further quantity of furan (1.3 ml, 17.8 mmol) is added and stirring continued for 18 hours, and then a further quantity of furan (1.3 ml, 17.8 mmol) is added and the mixture is stirred for 48 hours, and then allowed to stand at room temperature for 5 days. The reaction mixture is dissolved in methanol and concentrated under reduced pressure. The residue is purified by column chromatography on silica gel to give (1RS,2SR,6RS,7SR)-4-(5-bromo-2-ethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione.

¹H NMR (400 MHz, d₄-MeOH) δ_(H) 7.37 (1H, dd), 7.17 (1H, d), 7.14 (1H, d), 6.54 (2H, s), 4.96 (2H, s), 2.79 (2H, s), 2.44 (2H, q), 1.06 (3H, t)

Example 14 Preparation of (1RS, 2SR,6RS,7SR)-4-(5-bromo-2-ethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione

A solution of (1RS, 2SR,6RS,7SR)-4-(5-bromo-2-ethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]-dec-8-en-3,5-dione (3.00 g, 8.6 mmol) in methanol (250 ml) is hydrogenated at 3.5 bar over 5% palladium on carbon for 2 hours at room temperature. The catalyst is removed by filtration through diatomaceous earth and the solvent is evaporated under reduced pressure to give (1RS,2SR,6RS,7SR)-4-(5-bromo-2-ethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione.

¹H NMR (400 MHz, d_(a)-MeOH) δ_(H) 7.34 (1H, dd), 7.15 (2H, d), 4.59 (2H, s), 2.78 (2H, s), 2.43 (2H, q), 1.81-1.78 (2H, m), 1.66-1.61 (2H, m), 1.06 (3H, t).

Example 15 Preparation of (1RS,2RS,6SR,7SR)-8-bromo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]dec-8-en-3,5-dione

3-Bromofuran (5.2 g, 56 mmol) and magnesium iodide (1.5 g, 5.6 mmol) are added to 2-(2,4,6-trimethylphenyl)cyclopent-4-ene-1,3-dione (4.0 g, 18.7 mmol) and the mixture is stirred at room temperature for 2 days; small quantities of dichloromethane are added when required to aid stirring. The reaction mixture is allowed to stand at room temperature for 17 hours, then concentrated under reduced pressure. The residue is purified by column chromatography on silica gel to give (1RS, 2RS,6SR,7SR)-8-bromo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]dec-8-en-3,5-dione.

¹H NMR (400 MHz, CDCl₃) δ_(H) 6.87 (2H, s), 6.40 (1H, d), 4.95 (1H, s), 4.82 (1H, s), 2.90 (1H, d), 2.81 (1H, d), 2.25 (3H, s), 2.07 (3H, s), 2.03 (3H, s).

Example 16 Preparation of (1RS,2SR,6RS,7RS)-8-(4-fluorophenyl)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione

A mixture of (1RS,2RS,6SR,7SR)-8-bromo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]dec-8-en-3,5-dione (300 mg, 0.82 mmol), 4-fluorophenylboronic acid (171 mg, 1.22 mmol), sodium 2′-dicyclohexylphosphino-2,6-dimethoxy-1,1-biphenyl-3-sulfonate hydrate (17 mg, 0.03 mmol), potassium phosphate (522 mg, 2.5 mmol) and palladium acetate (4 mg, 0.02 mmol) in water (8 ml) are heated for 150° C. for 25 minutes under microwave irradiation. The mixture is cooled to room temperature and dilute aqueous hydrochloric acid is added. The mixture is filtered and the filtrate is extracted with ethyl acetate. The organic extracts are combined, dried over anhydrous magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure. Purification by column chromatography on silica gel gives (1RS,2SR,6RS,7RS)-8-(4-fluorophenyl)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione.

¹H NMR (400 MHz, CDCl₃) δ_(H) 7.35-7.32 (2H, m), 6.86 (1H, s), 6.85 (1H, s), 6.82-6.77 (2H, m), 6.37 (1H, d), 5.31 (1H, s), 5.03 (1H, d), 2.82-2.78 (2H, m), 2.25 (3H, s), 2.07 (3H, s), 2.05 (3H, s).

Example 17 Preparation of (1RS,2SR,6RS,7SR,8SR)-8-(4-fluorophenyl)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione

A suspension of (1RS,2SR,6RS,7RS)-8-(4-fluorophenyl)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione (99 mg, 0.26 mmol) in methanol (20 ml) is hydrogenated at 3 bar over 5% palladium on carbon for 5 hours at room temperature. The catalyst is removed by filtration through diatomaceous earth and the solvent is evaporated under reduced pressure to give (1RS,2SR,6RS,7SR,8SR)-8-(4-fluorophenyl)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2g)]decane-3,5-dione.

¹H NMR (400 MHz, CDCl₃) δ_(H) 7.39 (2H, dd), 7.11 (2H, t), 6.86 (1H, s), 6.85 (1H, s), 4.73 (1H, d), 4.68 (1H, d), 3.63-3.58 (1H, m), 2.94 (1H, d), 2.75 (1H, d), 2.38-2.30 (1H, m), 2.25 (3H, s), 2.08 (3H, s), 2.03 (3H, s), 1.92 (1H, dd).

Example 18 Preparation of (1RS,2SR,6RS,7SR,8RS)-8-(3-fluorophenyl)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione

Bis(triphenylphosphine)palladium diacetate (20 mg, 0.024 mmol), 1-fluoro-3-iodo-benzene (104 mg, 0.47 mmol) and piperidine (0.16 ml, 1.6 mmol) are added to a solution of (1RS,2SR,6RS,7SR)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione (0.20 g, 0.71 mmol) in dry N,N-dimethylformamide (2 ml). Formic acid (0.06 ml, 1.6 mmol) is added and the reaction mixture is heated at 50° C. for 2 hours. The reaction mixture is cooled to room temperature, water (1 ml) and dichloromethane (1 ml) are added, and the mixture is stirred for 1 hour. The two phases are separated, the organic phase collected and the solvent is evaporated. The residue is purified by preparative reverse-phase HPLC to give (1RS,2SR,6RS,7SR,8RS)-8-(3-fluorophenyl)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione.

¹H NMR (400 MHz, CDCl₃) δ_(H) 7.75-7.66 (1H, m), 7.25-7.21 (1H, m), 7.06-7.02 (2H, m), 6.88 (1H, s), 6.87 (1H, s), 4.83 (1H, br. s), 4.59 (1H, s), 3.00-2.98 (1H, m), 2.83-2.70 (2H, br. s), 2.25 (3H, s), 2.20-2.16 (1H, m), 2.09 (3H, s), 2.08 (3H, s), 1.92-1.89 (1H, m).

Example 19 Preparation of (1RS,2SR,6RS,7SR,8RS)-8-[2,6-bis(trifluoromethyl)pyridin-4-yl]-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione

A mixture of (1RS,2SR,6RS,7SR)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]dec-8-en-3,5-dione (400 mg, 1.4 mmol), 2,6-bis(trifluoromethyl)-4-chloropyridine (531 mg, 1.4 mmol), palladium acetate (16 mg, 0.07 mmol), 2′-dicyclohexylphosphino-2,6-dimethoxy-1,1′-biphenyl (67 mg, 0.14 mmol), potassium formate (353 mg, 4.2 mmol), tetrabutylammonium chloride (389 mg, 1.4 mmol) and copper iodide (53 mg, 0.28 mmol) in dry N,N-dimethylformamide (6 ml) are heated, at 150° C. for 30 minutes under microwave irradiation. Purification by preparative reverse-phase HPLC gives (1RS,2SR,6RS,7SR,8RS)-8-[2,6-bis(trifluoromethyl)pyridin-4-yl]-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione.

¹H NMR (400 MHz d₄-MeOH) δ_(H) 7.81 (1H, s), 7.26 (1H, s), 6.92 (1H, s), 6.90 (1H, s), 4.91 (1H, d), 4.64 (1H, s), 3.19-3.17 (1H, m), 2.99-2.95 (2H, m), 2.32-2.27 (1H, m), 2.26 (3H, s), 2.09 (3H, s), 2.07 (3H, s), 1.93-1.90 (1H, m).

Example 20 Preparation of (1RS,2SR,6RS,7SR, 8RS)-4-(2,4,6-trimethylphenyl)-8-vinyl-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione

A mixture of (1RS,2SR,6RS,7SR)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-3,5-dione (510 mg, 1.8 mmol), vinyl iodide (280 mg, 1.8 mmol), palladium acetate (20 mg, 0.09 mmol), sodium formate (454 mg, 5.4 mmol) and tetrabuylammonium chloride (500 mg, 1.8 mmol) in dry N,N-dimethylformamide (15 ml) are heated at 150° C. for 20 minutes under microwave irradiation. The mixture is cooled to room temperature and partitioned between water and ethyl acetate. The organic extracts are combined, dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure. The residue is purified by column chromatography on silica gel to give (1RS,2SR,6RS,7SR,8RS)-4-(2,4,6-trimethylphenyl)-8-vinyl-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione.

¹H NMR (400 MHz, CDCl₃) δ_(H) 6.90-6.89 (2H, m), 5.80-5.71 (1H, m), 5.05-4.97 (2H, m), 4.68 (1H, d), 4.44 (1H, s), 2.81-2.76 (2H, m), 2.51-2.46 (1H, m), 2.26 (3H, s), 2.07 (3H, s), 2.06 (3H, s), 1.89-1.84 (1H, m), 1.67-1.62 (1H, m).

Example 21 Preparation of methyl [(1RS,2SR,6RS,7SR. 8RS)-3,5-dioxo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-yl]acrylate

Benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexyl-phosphine)ruthenium (14 mg, 0.016 mmol) is added to a suspension of (1RS,2SR,6RS,7SR,8RS)-4-(2,4,6-trimethylphenyl)-8-vinyl-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione (100 mg, 0.32 mmol) and methyl acrylate (0.03 ml, 0.35 mmol) in dichloromethane (1 ml) and the mixture is stirred at reflux for 2 hours. The reaction mixture is cooled to room temperature, the solvent evaporated under reduced pressure and the residue is purified by column chromatography on silica gel to give methyl [1RS,2SR,6RS,7SR,8RS)-3,5-dioxo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]dec-8-yl]acrylate. Proton NMR indicates the product comprises a mixture of E- and Z-isomers.

E-Isomer: ¹H NMR (400 MHz, CDCl₃) δ_(H) 6.80 (2H, s), 6.74 (1H, dd), 5.91 (1H, d), 4.58 (1H, d), 4.30 (1H, s), 3.33 (3H, s), 2.85-2.77 (3H, m), 2.21 (3H, s), 1.97 (3H, s), 194 (3H, s), 1.94-1.91 (1H, m), 1.59-1.54 (1H, m).

Example 22 Preparation of (1RS,2SR,6SR,7SR)-1-hydroxymethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-ene-3,5-dione

Furfuryl alcohol (4 ml, 46.7 mmol) is added to 2-(2,4,6-trimethylphenyl)cyclopent-4-ene-1,3-dione (2.0 g, 9.3 mmol) and MgI₂ (520 mg, 1.86 mmol) and the reaction is stirred for 17 hours. The reaction mixture is adsorbed onto silica gel and purified by column chromatography on silica gel to give (1RS,2SR,6RS,7SR)-1-hydroxymethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]dec-8-ene-3,5-dione.

¹H NMR (400 MHz, CDCl₃) δ_(H) 6.87 (2H, s), 6.49 (1H, d), 6.44 (1H, d), 4.96 (1H, d), 3.98 (1H, d), 3.85 (1H, d), 2.82-2.78 (2H, m), 2.24 (3H, s), 2.08 (3H, s), 2.05 (3H, s).

Example 23 Preparation of tert-butyl carbamic acid [(1RS,2SR,6RS,7SR)-3,5-dioxo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-1-yl]methyl ester

Step 1: Preparation of (1RS,2SR,6SR,7SR)-5-benzyloxy-7-hydroxymethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]deca-4,8-dien-3-one and (1RS,2SR,6RS,7SR)-5-benzyloxy-1-hydroxymethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]deca-4,8-dien-3-one

Benzyl bromide (0.72 ml, 6.1 mmol) is added to a mixture of potassium carbonate (840 mg, 6.1 mmol) and (1RS,2SR,6RS,7SR)-1-hydroxymethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]dec-8-ene-3,5-dione (1.80 g, 5.8 mmol) in acetone (80 ml), and the reaction mixture is heated at reflux for 4 hours. The reaction mixture is cooled to room temperature, diluted with water and extracted with ethyl acetate. The organic extracts are combined, dried over anhydrous magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure. The residue is purified by column chromatography on silica gel to give a mixture of (1RS,2SR,6SR,7SR)-5-benzyloxy-7-hydroxymethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]deca-4,8-dien-3-one and (1RS,2SR,6RS,7SR)-5-benzyloxy-1-hydroxymethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]deca-4,8-dien-3-one.

Step 2: Preparation of tert-butyl carbamic acid [(1RS,2RS,6RS,7SR)-3-benzyloxy-5-oxo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]deca-4,8-dien-1-yl]methyl ester and tert-butyl carbamic acid [(1RS,2SR,6RS,7SR)-5-benzyloxy-3-oxo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]deca-4,8-dien-1-yl]methyl ester

Sodium hydride (60 mg, 1.97 mmol) is added to a cooled (0° C.) mixture of (1RS,2SR,6SR,7SR)-5-benzyloxy-7-hydroxymethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]deca-4,8-dien-3-one and (1RS,2SR,6RS,7SR)-5-benzyloxy-1-hydroxymethyl-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]deca-4,8-dien-3-one (265 mg, 0.66 mmol) in tetrahydrofuran (10 ml). The mixture is stirred for a few minutes and then tert-butyl isocyanate (0.15 ml, 1.32 mmol) is added. The reaction is allowed warm to room temperature and stirred for 17 hours. The mixture is partitioned between water and ethyl acetate, and the organic solutions are combined, dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated. The residue is purified by column chromatography on silica gel to give a mixture of tert-butyl carbamic acid [(1RS,2RS,6RS,7SR)-3-benzyloxy-5-oxo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]deca-4,8-dien-1-yl]methyl ester and tert-butyl carbamic acid [(1RS,2SR,6RS,7SR)-5-benzyloxy-3-oxo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]deca-4,8-dien-1-yl]methyl ester.

Step 3: Preparation of tert-butyl carbamic acid [(1RS,2SR,6RS,7SR)-3,5-dioxo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-1-yl]methyl ester

A suspension of a mixture of [(1RS,2RS,6RS,7SR)-3-benzyloxy-5-oxo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]deca-4,8-dien-1-yl]methyl ester and tert-butyl carbamic acid [(1RS, 2SR,6RS,7SR)-5-benzyloxy-3-oxo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]deca-4,8-dien-1-yl]methyl ester (147 mg, 0.29 mmol) in methanol (20 ml) is hydrogenated at 3 bar over 5% palladium on carbon for 5 hours. The catalyst is removed by filtration and the filtrate is concentrated under reduced pressure to give tert-butyl carbamic acid [(1RS,2SR,6RS,7SR)-3,5-dioxo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-8-en-1-yl]methyl.

¹H NMR (400 MHz, CDCl₃) δ_(H) 6.83 (2H, s), 5.02 (1H, s), 4.72 (1H, d), 4.65 (1H, d), 4.12 (1H, d), 2.83 (1H, d), 2.70 (1H, d), 2.23 (3H, s), 2.07 (3H, s), 2.06 (3H, s), 1.86-1.80 (2H, m), 1.57-1.45 (2H, m), 1.29 (9H, s).

Example 24 Preparation of (1RS,2SR,6RS,7SR)-4-(4-bromo-2-ethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione

Step 1: Preparation of 4-bromo-2-ethylphenyllead triacetate

Dry chloroform (30 ml) is added to a mixture of lead tetraacetate (8.52 g, 19.3 mmol) and mercuric diacetate (0.28 g, 0.875 mmol) under an atmosphere of nitrogen, and the reaction mixture is stirred and heated to 40° C. 4-Bromo-2-ethylphenylboronic acid (4.0 g, 17.5 mmol) is added in one portion and the mixture is stirred at 40° C. for 4 hours. The reaction mixture is cooled to 0° C., and potassium carbonate (2.66 g, 19.3 mmol) is added portionwise. The mixture is stirred for 5 minutes, then filtered through a small plug of diatomaceous earth, washing with chloroform. The filtrate concentrated under reduced pressure to give 4-bromo-2-ethylphenyllead triacetate.

Step 2: Preparation of (1RS,2SR,6RS,7SR)-4-(4-bromo-2-ethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione

4-Dimethylaminopyridine (3.67 g, 30.0 mmol) and toluene (10 ml) are added to a solution of (1RS,2SR,6RS,7SR)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione (1.0 g, 6.0 mmol) in chloroform (40 ml) and the reaction mixture is heated to 80° C. 4-Bromo-2-ethylphenyllead triacetate (5.13 g, 9.04 mmol) is added portionwise over 20 minutes, and once the addition is complete the reaction mixture is stirred at 80° C. for a further 4 hours. The mixture is cooled to room temperature, 2 M aqueous hydrochloric acid (40 ml) is added, and the mixture is stirred vigorously for 15 minutes, then filtered through a small plug of diatomaceous earth, washing with 40 ml dichloromethane. The organic phase is separated, and the aqueous phase is extracted with dichloromethane (2×20 ml). The organic solutions are combined, dried over anhydrous magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure. The residue is purified by column chromatography on silica gel to give (1RS,2SR,6RS,7SR)-4-(4-bromo-2-ethylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]decane-3,5-dione.

¹H NMR (400 MHz, CDCl₃) δ_(H) 7.39 (1H, dd), 7.27-7.33 (1H, m), 6.97 (1H, dd), 4.68 (2H, m), 2.74 (2H, br. s), 2.48 (2H, q), 1.78-1.87 (2H, m), 1.56 (2H, m), 1.11 (3H, t).

Additional compounds in Table T1 below were prepared by similar methods using appropriate starting materials. It should be noted that certain compounds of the invention exist as a mixture of isomers noted above, under the conditions used to obtain the ¹H NMR data. Where this has occurred, the characterising data are reported for all isomers present at ambient temperature in the specified solvent. Unless otherwise stated, proton NMR spectra were recorded at ambient temperature. Compounds characterised by HPLC-MS were analysed using one of two methods described below.

Method A

Compounds characterised by HPLC-MS were analysed using an Waters 2777 injector with a 1525 micro pump HPLC equipped with a Waters Atlantis dC18 IS column (column length 20 mm, internal diameter of column 3 mm, particle size 3 micron), Waters 2996 photodiode array, Waters 2420 ELSD and Micromass ZQ2000. The analysis was conducted using a three minute run time, according to the following gradient table:

Time Solvent A Solvent B (mins) (%) (%) Flow (ml/mn) 0.00 95.0 5 1.300 2.50 0.0 100 1.300 2.80 0.00 100 1.300 2.90 95.0 5 1.300 Solvent A: H₂O with 0.05% TFA Solvent B: CH₃CN with 0.05% TFA

Method B

Compounds characterised by HPLC-MS were analysed using a Waters 2795 HPLC equipped with a Waters Atlantis dC18 column (column length 20 mm, internal diameter of column 3 mm, particle size 3 micron, temperature 40° C.), Waters photodiode array and Micromass ZQ2000. The analysis was conducted using a three minute run time, according to the following gradient table:

Time Solvent A Solvent B Flow (mins) (%) (%) (ml/mn) 0.00 90.0 10.0 2.00 0.25 90.0 100 2.00 2.00 10.0 90.0 2.00 2.50 10.0 90.0 2.00 2.60 90.0 10.0 2.00 3.0 90.0 10.0 2.00 Solvent A: H₂O containing 0.1% HCOOH Solvent B: CH₃CN containing 0.1% HCOOH

The characteristic values obtained for each compound were the retention time (rt, recorded in minutes) and the molecular ion (typically the cation MH⁺), as listed in Table T1.

TABLE T1 Compound ¹H nmr (CDCl₃ unless stated) or other physical Number Structure data T1

δ_(H) 6.88-6.87 (2H, m), 4.55-4.54 (2H, m), 2.62 (2H, s), 2.36-2.27 (7H, m), 1.69-1.67 (2H, m), 1.40-1.39 (2H, m), 1.03 (6H, q). T2

δ_(H) 6.88 (2H, m), 4.58 (2H, s), 2.65 (2H, m), 2.38- 2.32 (2H, m), 2.26 (3H, s), 2.02 (3H, s), 1.76- 1.71 (2H, m), 1.45 (2H, m), 1.04 (3H, q). T3

δ_(H) 6.86 (1H, s), 6.85 (1H, s), 4.68-4.67 (2H, m), 2.74 (2H, s), 2.24 (3H, s), 2.10 (3H, s), 2.08 (3H, s), 1.83-1.80 (2H, m), 1.56-1.54 (2H, m). T4

δ_(H) 6.94 (2H, s) ,6.44 (2H, s), 5.04 (2H, s), 2.81- 2.73 (2H, m), 2.41-2.35 (4H, m), 2.30 (3H, s), 1.10-1.02 (6H, m). T5

δ_(H) 6.94 (1H, s), 6.93 (1H, s), 4.64-4.63 (2H, m), 2.73 (2H, s), 2.59 (2H, q), 2.41-2.31 (4H, m), 1.77 (2H, m), 1.48 (2H, m), 1.22 (3H, t), 1.06 (6H, m). T6

δ_(H) 6.98 (1H, s), 6.97 (1H, s), 2.64-2.59 (2H, brs), 2.25 (3H, s), 2.03 (6H, s), 1.66 (4H, s), 1.50 (6H br s). T7

δ_(H) 6.95 (1H, s), 6.47 (1H, br s), 3.00 (1H, d), 2.68- 2.66 (1H, m), 2.44-2.31 (7H, m), 1.77-1.71 (4H, m), 1.58 (3H, s), 1.55 (3H, s), 1.08 (6H, q). T8

δ_(H) 6.95 (s), 4.69 (d), 4.64 (d), 3.05 (d), 2.91 (d), 2.81 (d), 2.59 (d), 2.44-2.32 (m), 2.31 (s), 2.00- 1.93 (m), 1.67-1.62 (m), 1.61 (s), 1.58 (s), 1.10- 1.05 (m). T9

δ_(H) 6.92 (2H, s), 6.47 (1H, s), 6.32 (0.5H, s), 6.28 (0.5H, s), 5.14 (0.5H, s), 4.97 (0.5H, br s), 3.06 (0.5H, br s), 2.86 (0.5H, s), 2.80(0.5H br s), 2.50 (0.5H, br s), 2.28 (3H, s), 2.12 (6H, s), 1.70 (3H, br s). T10

δ_(H) 6.95 (2H, s), 4.75 (2H, br), 3.40 (2H, br), 2.45 (2H, q), 2.35(2H, q), 2.30 (3H, s), 1.80 (4H, m), 1.15 (3H, t), 1.05 (3H, t). T11

δ_(H) 6.70 (2H, s), 6.24 (1H, s), 4.79 (1H, s), 4.73 (1H, s), 2.67 (1H, br s), 2.56 (1H, d), 2.17-2.08 (7H, m), 0.87-0.77 (6H, m), 0.00 (9H, s). T12

δ_(H) 6.94 (2H, s), 6.66 (0.5H, s), 6.62 (0.5H, s), 5.14- 5.02 (2H, m), 3.42(1H, s), 3.10(0.5H, s), 3.00 (0.5H, s), 2.86 (0.5H, s), 2.77 (0.5 H, s), 2.38- 2.31 (7H, m), 1.10-1.01 (6H, m). T13

δ_(H) 6.95 (2H, s), 6.60 (1H, s), 6.53-6.51 (1H, m), 5.07 (1H, s), 4.14-4.00 (2H, m), 3.10-2.90 (br m, 2H), 2.42-2.28 (7H, m), 1.11-1.04 (6H, m). T14

δ_(H) 6.88 (2H, s), 4.57 (1H, d), 3.86 (1H, d), 3.73 (1H, d), 3.23 (1H, s), 2.35-2.27 (7H, m), 1.86- 1.53 (4H, m), 1.06-1.00 (6H, m). T15

δ_(H) 6.94 (1H, s), 6.93 (1H, s), 4.86 (1H, s), 4.79 (1H, d), 4.76 (1H, s), 3.50 (1H, d), 2.96 (1H, s), 2.78 (1H, s), 2.50-2.25 (9H, m), 1.24-1.18 (3H, m), 1.09-1.02 (6H, m). T16

δ_(H) 6.92 (2H, s), 5.00 (1H, d), 4.96 (1H, s), 4.93 (1H, s), 4.37-4.32 (2H, m), 3.78 (1H, d), 2.96 (1H, s), 2.61 (1H, s), 2.34-2.30 (7H, m), 1.39- 1.35 (3H, m), 1.07-1.00 (6H, m). T17

δ_(H) 8.40 (1H, s), 6.93 (1H, s), 6.92 (1H, s), 4.78 (1H, d), 4.01 (1H, d), 3.75 (1H, d), 3.52 (3H, s), 3.11 (1H, d), 2.81 (1H, d), 2.44-2.31 (4H, m), 2.30 (3H, s), 2.00-1.93 (2H, m), 1.75-1.70 (2H, m), 1.09-1.05 (6H, m). T18

δ_(H) 6.88 (1H, s), 6.87 (1H, s), 4.66 (1H, d), 3.94 (1H, d), 3.77 (1H, d), 3.65-3.52 (2H, m), 2.88 (1H, s), 2.80 (1H, d), 2.39-2.26 ((7H, m), 1.94- 1.90 (2H, m), 1.65-1.60 (4H, m), 1.20 (3H, t), 1.05-1.00 (6H, m). T19

δ_(H) 6.92 (1H, s), 6.91 (1H, s), 4.75 (2H, s), 4.69 (1H, s), 4.04-3.96 (2H, m), 3.64-3.61 (2H, m), 2.94 (1H, br s), 2.81 (1H, d), 2.42-2.30 (4H, m), 2.30 (3H, s), 2.00-1.86 (2H, m), 1.69-1.54 (2H, m), 1.22-1.19 (3H, m), 1.08-1.04 (8H, m). T20

δ_(H) 7.29-7.26 (2H, m), 7.05 (2H, d), 6.85 (1H, s), 6.84 (1H, s), 6.39 (1H, d), 5.32 (1H, s), 5.02 (1H, d), 2.79-2.75 (2H, m), 2.33 (3H, s), 3.23 (3H, s), 2.07 (3H, s), 2.04 (3H, s). T21

δ_(H) 6.87 (2H, s), 5.44 (1H, v. br s), 4.71-4.64 (2H, m), 4.26-4.23 (1H, m), 3.11-3.06 (2H, m), 2.90 (1H, br s), 2.81 (1H, d), 2.38-2.27(4H, m), 2.25 (3H, s), 1.93-1.82 (2H, m), 1.66-1.52 (2H, m), 1.50-1.43 (2H, m), 1.01 (6H, t), 0.87 (3H, t). T22

δ_(H) 7.21 (1H, d), 6.93 (1H, dd), 6.84 (2H, s), 6.30 (1H, s), 5.24 (1H, s), 5.04 (1H, s), 2.82-2.81 (1H, m), 2.78-2.77 (1H, m), 2.28 (3H, s with fine splitting) 2.22 (3H, s), 2.07 (3H, s), 2.04 (3H, s). T23

δ_(H) 7.33 (2H, d), 6.86-6.81 (4H, m), 6.35 (1H, s), 5.32 (1H, s), 5.04 (1H, s), 3.80 (3H, s), 2.83-2.82 (1H, m), 2.77 (1H, br s), 2.24 (3H, s), 2.07 (3H, s), 2.05 (3H, s). T24

δ_(H) 7.35-7.32 (2H, m), 6.86 (1H, s), 6.85 (1H, s), 6.82-6.77 (2H, m), 6.37 (1H, d), 5.31 (1H, s), 5.03 (1H, d), 2.82-2.78 (2H, m), 2.25 (3H, s), 2.07 (3H, s), 2.05 (3H, s). T25

δ_(H) 7.25-7.17 (4H, m), 6.86 (1H, s), 6.84 (1H, s), 4.73 (1H, d), 4.68 (1H, d), 3.61-3.56 (1H, m), 2.90 (1H, d), 2.80 (1H, d), 2.35-2.20 (4H, m). 2.24 (3H, s), 2.07 (3H, s), 2.02 (3H, s), 1.92 (1H, dd). T26

δ_(H) 7.38-7.36 (2H, m), 7.22-7.20 (2H, m), 6.86 (2H, s), 6.58 (1H, d), 5.38 (1H, d), 5.11 (1H, s), 2.90 (1H, m), 2.84(1H, m), 2.47 (3H, s), 2.24 (3H, s), 2.08 (6H, s). T27

δ_(H) 6.92 (2H, s), 4.62 (1H, d), 4.29-4.27 (1H, m), 4.10-4.03 (2H, m), 3.93-3.90 (1H, m), 2.84 (1H, d), 2.77 (1H, d), 2.38-2.29 (4H, m), 2.30 (3H, s), 1.96-1.88 (2H, m), 1.59-1.51 (2H, m), 1.07- 1.03 (6H, m). T28

δ_(H) 7.39 (2H, dd), 7.11 (2H, t), 6.86 (1H, s), 6.85 (1H, s), 4.73 (1H, d), 4.68 (1H, d), 3.63-3.58 (1H, m), 2.94 (1H, d), 2.75 (1H, d), 2.38-2.30 (1H, m), 2.25 (3H, s), 2.08 (3H, s), 2.03 (3H, s), 1.92 (1H, dd). T29

δ_(H) 6.82 (2H, s), 4.54 (1H, d), 3.85 (1H, d), 3.67 (1H, d), 3.30 (3H, s), 2.90 (1H, d), 2.78 (1H, d), 2.20 (3H, s), 2.03 (3H, s), 1.99 (3H, s), 1.93 (1H, dd), 1.87-1.81 (1H, m), 1.70-1.63 (1H, m), 1.58- 1.54 (1H, m). T30

δ_(H) 6.87 (1H, s), 6.86 (1H, s), 4.87-4.81 (1H, m), 4.67-4.65 (1H, m), 4.08-3.93 (2H, m), 3.66- 3.58 (2H, m), 2.89-2.84 (1H, m), 2.76-2.73 (1H, m), 2.25 (3H, s), 2.09 (3H, s), 2.06 (3H, s), 1.95- 1.84 (2H, m), 1.71-1.59 (2H, m), 1.26-1.17 (3H, m). T31

δ_(H) 6.88 (1H, s), 6.87 (1H, s), 4.67 (1H, t), 3.97 (1H, d), 3.81 (1H, d), 3.70-3.62 (1H, m), 3.60- 3.54 (1H, m), 2.87-2.82 (2H, m), 2.25 (3H, s), 2.10 (3H, s), 2.06 (3H, s), 1.99-1.94 (2H, m), 1.69-1.64 (2H, m), 1.23 (3H, t). T32

δ_(H) 7.20-7.18 (2H, m), 7.12-7.10(2H, m), 6.88 (1H, s), 6.85 (1H, s), 4.71 (2H, t), 3.55-3.50 (1H, m), 2.77(1H, d), 2.73 (1H, d), 2.48 (3H, s), 2.32- 2.25 (1H, m), 2.23 (3H, s), 2.07 (3H, s), 2.01 (3H, s), 1.72 (1H, dd). T33

δ_(H) 6.93 (2H, s), 6.88 (2H, s), 6.36 (1H, d), 5.13 (1H, d), 5.01 (1H, s), 3.13 (1H, d), 2.96 (1H, d), 2.29 (12H, s), 2.11 (3H, s), 2.09 (3H, s). T34

δ_(H) 2.82 (2H, s), 6.19 (2H, s), 2.51 (2H, br s), 2.22 (3H, s), 2.05 (3H, s), 2.04 (3H, s), 1.57 (6H, s). T35

δ_(H) 6.88 (1H, s), 6.87 (1H, s), 4.73-4.69 (2H, m), 4.29 (1H, d), 3.14-3.09 (2H, m), 2.93 (1H, d), 2.85 (1H, d), 2.25 (3H, s), 2.09 (3H, s), 2.06 (3H, s), 1.97-1.86 (2H, m), 1.71-1.59 (2H, m), 1.54- 1.47 (2H, m), 0.91 (3H, t). T36

δ_(H) 6.83 (2H, s), 5.02 (1H, s), 4.72 (1H, d), 4.65 (1H, d), 4.12 (1H, d), 2.83 (1H, d), 2.70 (1H, d), 2.23 (3H, s), 2.07 (3H, s), 2.06 (3H, s), 1.86-1.80 (2H, m), 1.57-1.45 (2H, m), 1.29 (9H, s). T37

LC-MS (Method A) ES⁺: MH⁺ = 313; rt = 1.07 mins T38

LC-MS (Method A) ES⁺: MH⁺ = 313; rt = 1.07 mins T39

LC-MS (Method A) ES⁺: MH⁺ = 327; rt = 1.23 mins T40

LC-MS (Method A) ES⁺: MH⁺ = 311; rt = 1.34 mins T41

LC-MS (Method A) ES⁺: MH⁺ = 343; rt = 1.35 mins T42

LC-MS (Method A) ES⁺: MH⁺ = 353; rt = 1.79 mins T43

LC-MS (Method A) ES⁺: MH⁺ = 371; rt = 1.50 mins T44

LC-MS (Method A) ES⁺: MH⁺ = 297; rt = 1.25 mins T45

δ_(H) 6.86 (2H, s), 4.61-4.58 (2H, m), 4.43 (1H, d), 4.07 (1H, d), 3.95 (1H, d), 2.98-2.85 (2H, m), 2.24 (3H, s), 2.08 (3H, s), 2.06 (3H, s), 1.91-1.87 (2H, m), 1.76-1.70 (1H, m), 1.65-1.59 (1H, m). T46

δ_(H) 6.93 (2H, s), 4.75 (1H, d), 4.72 (1H, s), 4.38 (1H, dd), 3.93 (1H, d), 3.68 (1H, d), 2.90 (1H, d), 2.38-2.31 (7H, m), 1.08-1.01 (6H, m). T47

δ_(H) 6.82 (2H, s), 4.50-4.45 (2H, m), 3.36-3.34 (1H, m), 3.26-3.24 (4H, m), 2.92 (1H, d), 2.47 (1H, d), 2.41-2.36 (1H, m), 2.23 (3H, s), 2.02 (6H, s), 1.95-1.88 (1H, m), 1.00 (1H, dd). T48

δ_(H) 6.84-6.83 (2H, m), 4.47 (1H, d), 2.63 (1H, d), 2.41 (1H, d), 2.23 (3H, s), 2.04 (3H, s), 2.01 (3H, s), 1.86-1.83 (1H, m), 1.55-1.46 (3H, m), 1.48 (3H, s). T49

δ_(H) 6.85 (2H, s), 4.55 (1H, d), 3.84 (1H, d), 3.75 (1H, d), 2.76-2.70 (2H, m), 2.23 (3H, s), 2.03 (6H, s). T50

δ_(H) 6.83-6.82 (2H, m), 4.48-4.45 (2H, m), 3.35- 3.34 (1H, m), 3.26-3.24 (1H, m), 2.93 (1H, d), 2.48 (1H, d), 2.23 (3H, s), 2.02 (6H, s), 2.42- 2.36 (1H, m), 1.94-1.88 (1H, m), 1.01 (1H, dd). T51

δ_(H) 6.85 (2H, s), 4.55 (1H, d), 4.03 (1H, q), 2.76 (1H, d), 2.72 (1H, d), 2.23 (3H, s), 2.04 (3H, s), 2.03 (3H, s), 1.84-1.70 (2H, m), 1.58-1.41 (2H, m), 1.24 (3H, d). T52

δ_(H) 6.82 (1H, s), 6.81 (1H, s), 4.42 (1H, d), 2.53- 2.48 (2H, m), 2.22 (3H, s), 2.00 (3H, s), 1.98 (3H, s), 1.93-1.86 (1H, m), 1.77-1.70 (2H, m), 1.54- 1.41 (3H, m), 1.03 (3H, t). T53

δ_(H) 6.83 (2H, s), 4.49 (1H, d), 3.00-2.92 (2H, m), 2.62-2.58 (2H, m), 2.23 (3H, s) ,2.14 (3H, s), 2.02 (3H, s), 2.00 (3H, s), 2.00-1.85 (2H, m), 1.52-1.47 (2H, m). T54

δ_(H) 6.84 (1H, s), 6.83 (1H, s), 4.45 (1H, d), 2.60- 2.56 (2H, m), 2.23 (3H, s), 2.04 (3H, s), 2.00 (3H, s), 1.93-1.88 (1H, m), 1.80-1.76 (1H, m), 1.69- 1.46 (4H, m), 1.35-1.26 (6H, m), 0.88-0.85 (3H, m). T55

δ_(H) 6.86 (2H, m), 3.11-3.00 (4H, m), 2.72 (1H, d), 2.25 (3H, s), 2.09 (3H, s), 2.05 (3H, s), 1.98- 1.89 (1H, m), 1.79-1.56 (3H, m), 1.33-1.25 (6H, m). T56

δ_(H) 7.28-7.17 (5H, m), 6.89 (1H, s), 6.88 (1H, s), 4.72 (1H, d), 4.53 (1H, s), 2.89 (1H, dd), 3.02 (1H, d), 2.96 (1H, d), 2.32-2.30 (1H, m), 2.27 (3H, s), 2.07 (6H, s), 1.90-1.85 (1H, m). T57

δ_(H) 7.26-7.23 (2H, m), 6.88-6.85 (4H, m), 4.74 (1H, d), 4.40 (1H, s), 3.79 (3H, s), 3.10 (1H, dd), 3.02 (1H, d, 2.96 (1H, d), 2.32-2.30 (1H, m), 2.27 (3H, s), 2.07 (6H, s), 1.90-1.85 (1H, m). T58

LC-MS (Method A) ES⁺: MH⁺ = 327; rt = 1.10 mins T59

LC-MS (Method A) ES⁺: MH⁺ = 369; rt = 1.33 mins T60

LC-MS (Method A) ES⁺: MH⁺ = 365; rt = 1.77 mins T61

LC-MS (Method A) ES⁺: MH⁺ = 383; rt = 1.36 mins T62

δ_(H) 6.86 (2H, s), 4.48 (1H, d), 3.68-3.48 (2H, m), 2.81-2.74 (1H, m), 2.67 (1H, d), 2.23 (3H, s), 2.07 (3H, s), 2.04 (3H, s), 1.54 (3H, s), 1.27- 1.26 (1H, m), 1.04-1.01 (2H, m). T63

LC-MS (Method A) ES⁺: MH⁺ = 355; rt = 1.36 mins T64

LC-MS (Method A) ES⁺: MH⁺ = 343; rt = 1.37 mins T65

d₄-MeOH δ_(H) = 6.85 (2H, m), 4.51 (1H, d), 4.37 (1H, d), 3.14 (1H, d), 2.84 (1H, d), 2.28-2.24 (1H, m), 2.24 (3H, s), 2.13 (1H, dd), 2.04 (3H, s), 2.03 (3H, s), 1.13 (3H, d), 1.11-1.06 (1H, m). T66

δ_(H) 7.26-7.18 (4H, m), 6.85 (2H, s), 4.72 (1H, d), 4.40 (1H, s), 3.09 (1H, dd), 3.00 (1H, d), 2.94 (1H, d), 2.44 (3H, s), 2.29-2.24 (1H, m), 2.24 (3H, s), 2.05 (6H, s), 1.88-1.82 (1H, m). T67

δ_(H) 7.24-7.21 (1H, m), 6.94-6.93 (2H, m), 6.88 (2H, s), 4.75 (1H, d), 4.45 (1H, s), 3.52 (1H, dd), 3.05 (1H, d), 2.96 (1H, d), 2.35-2.29 (1H, m), 2.27 (3H, s), 2.08 (6H, s), 2.01-1.95 (1H, m). T68

Approximately 3:2 Mixture of Isomer A:Isomer B Isomer A: δ_(H) 6.86 (1H, s), 6.85 (1H, s), 4.55 (1H, d), 4.53 (1H, d), 3.50-3.42 (3H, m), 3.36-3.33 (1H, m), 3.02 (1H, d), 2.49-2.43 (2H, m), 2.25 (3H, s), 2.05 (6H, s), 2.01-1.94 (1H, m), 1.19 (3H, t), 1.06 (1H, dd).

T69

δ_(H) 6.85 (2H, s), 4.69(2H, s), 4.56-4.54 (2H, m), 3.76-3.55 (5H, m), 3.12 (1H, d), 2.83 (1H, d), 2.55-2.45 (1H, m), 2.24 (3H, s), 2.04 (3H, s), 1.24-1.15 (4H, m). T70

δ_(H) 7.34-7.31 (2H, m), 7.00 (2H, t), 6.85 (2H, s), 4.73 (1H, d), 4.39 (1H, s), 3.13 (1H, dd), 3.01 (1H, d), 2.95 (1H, d), 2.30-2.27 (1H, m), 2.24 (3H, s), 2.05 (6H, s), 1.87-1.81 (1H, m). T71

δ_(H) 7.21 (2H, d), 7.11 (2H, d), 6.88 (2H, s), 4.74 (1H, d), 4.42 (1H, s), 3.09 (1H, dd), 3.02 (1H, d), 2.96 (1H, d), 2.32 (3H, s), 2.29-2.24 (1H, m), 2.27 (3H, s), 2.08 (6H, s), 1.91-1.85 (1H, m). T72

δ_(H) 7.25-7.18 (4H, m), 6.86 (1H, s), 6.84 (1H, s), 4.73 (1H, d), 4.68 (1H, d), 3.61-3.56 (1H, m), 2.90 (1H, d), 2.80 (1H, d), 2.35 (3H, s), 2.32-2.28 (1H, m), 2.24 (3H, s), 2.07 (3H, s), 2.02 (3H, s), 1.92 (1H, dd). T73

δ_(H) 7.29-7.27 (3H, m), 7.22-7.19 (2H, m), 6.89 (1H, s), 6.88 (1H, s), 4.85 (1H, d), 4.61 (1H, s), 3.01 (1H, dd), 2.26 (3H, s), 2.19 (1H, dd), 2.10 (3H, s), 2.09 (3H, s), 2.00-1.96 (1H, m). T74

δ_(H) 6.90 (1H, s), 6.88 (1H, s), 6.86-6.82 (2H, m), 4.82-4.77 (2H, m), 3.12-3.05 (2H, m), 2.28- 2.86 (1H, m), 2.41-2.39 (1H, m), 2.26 (3H, s), 2.23 (3H, s), 2.11 (6H, s), 2.08 (3H, s), 2.01-1.97 (1H, m). T75

δ_(H) 7.79-7.76 (1H, m), 7.59-7.56 (1H, m), 7.28- 7.20 (2H, m), 6.90 (1H, s), 6.89 (1H, s), 4.88- 4.86 (1H, m), 4.67 (1H, s), 3.47-3.42 (1H, m), 3.14-3.00 (2H, m), 2.26 (3H, s), 2.25-2.21 (1H, m), 2.11 (3H, s), 2.09 (3H, s), 1.88-1.84 (1H, m). T76

δ_(H) 7.39-7.35 (1H, m), 7.19-7.16 (1H, m), 6.93- 6.83 (4H, m), 4.82 (1H, brs), 4.62 (1H, s), 3.48 (3H, s), 3.54 (1H, dd), 3.13-3.02 (2H, brm), 2.26 (3H, s), 2.17-2.13 (1H, m), 2.10 (3H, s), 2.09 (3H, s), 1.90-1.84 (1H, m). T77

δ_(H) 7.42 (1H, d), 7.21-7.12 (3H, m), 6.88 (1H, s), 6.87 (1H, s), 4.82 (1H, s), 4.82 (1H, d), 4.68 (1H, s), 3.51 (1H, dd), 2.47 (3H, s), 2.25 (3H, s), 2.23- 2.20 (1H, m), 2.10 (3H, s), 2.08 (3H, s), 1.85- 1.81 (1H, m). T78

δ_(H) 7.73-7.70 (2H, m), 7.59 (1H, d), 7.52-7.50 (1H, m), 7.31-7.28 (1H, m), 6.89 (1H, s), 6.88 (1H, s), 4.86 (1H, br S), 4.64 (1H, s), 3.42 (1H, br S), 3.13-3.05 (2H, m), 2.26 (3H, s), 2.66-2.24 (1H, m), 2.11 (3H, s), 2.08 (3H, s), 1.92-1.88 (1H, m). T79

δ_(H) 7.42-7.39 (1H, m), 7.18-7.11 (3H, m), 6.91 (1H, s), 6.90 (1H, s), 4.87-4.85 (1H, m), 4.74 (1H, s), 3.24-3.22 (1H, m), 3.13-3.07 (2H, m), 2.36 (3H, s), 2.34 (3H, s), 2.24-2.22 (1H, m), 2.19 (3H, s), 2.09 (3H, s), 1.88-186 (1H, m). T80

δ_(H) 7.79-7.73 (2H, m), 7.56 (1H, t), 7.35 (1H, t), 6.90 (1H, s), 6.89 (1H, s), 4.87 (1H, br s), 4.71 (1H, s), 3.47 (1H, br. s), 3.13-3.06 (2H, m), 2.42- 2.30 (1H, m), 2.26 (3H, s), 2.11 (3H, s), 2.09 (3H, s), 1.98-1.97 (1H, m). T81

δ_(H) 7.45-7.43 (1H, m), 7.18-7.16 (1H, m), 7.11- 7.08 (1H, m), 7.02-6.98 (1H, m), 6.89 (1H, s), 6.88 (1H, s), 4.85 (1H, d), 4.65 (1H, s), 3.44 (1H, br. s), 3.15-3.00 (2H, br. s), 2.26 (3H, s), 2.22- 2.17 (1H, m), 2.10 (3H, s), 2.09 (3H, s), 1.92- 1.88 (1H, s) T82

δ_(H) 7.47-7.96 (2H, m), 7.14-7.11 (2H, m), 6.90 (2H, s), 4.88 (1H, s), 4.57 (1H, s), 3.21 (1H, s), 2.94-2.74 (2H, br. s), 2.62, (3H, s), 2.26 (3H, s), 2.25-2.23 (1H, m), 2.11 (3H, s), 2.10 (3H, s), 2.01-1.93 (1H, m). T83

δ_(H) 7.75-7.66 (1H, m), 7.25-7.21 (1H, m), 7.06- 7.02 (2H, m), 6.88 (1H, s), 6.87 (1H, s), 4.83 (1H, br. s), 4.59 (1H, s), 3.00-2.98 (1H, m), 2.83- 2.70 (2H, br. s), 2.25 (3H, s), 2.20-2.16 (1H, m), 2.09 (3H, s), 2.08 (3H, s), 1.92-1.89 (1H, m). T84

δ_(H) 7.79-7.77 (1H, m), 7.21-7.18 (1H, m), 6.89- 6.86 (3H, m), 6.76-6.74 (1H, m), 4.83 (1H, d), 4.62 (1H, s), 3.80 (3H, s), 2.99 (1H, dd), 2.80- 2.70 (2H, br. s), 2.26 (3H, s), 2.18 (1H, dd), 2.10 (3H, s), 2.09 (3H, s), 1.97-1.95 (1H, m). T85

δ_(H) 7.54-7.46 (3H, m), 7.41-7.38 (1H, m), 6.87 (1H, s), 6.88 (1H, s), 4.85 (1H, d), 4.60 (1H, s), 3.06 (1H, dd), 2.25 (3H, s), 2.21 (1H, dd), 2.10 (3H, s), 2.08 (3H, s), 1.93-1.90 (1H, m). T86

δ_(H) 7.19-7.08 (3H, m), 7.03-7.07 (1H, m), 6.89 (1H, s), 6.88 (1H, s), 4.84 (1H, d), 4.60 (1H, s), 2.98 (1H, dd), 2.33 (3H, s), 2.26 (3H, s), 2.17 (1H, dd), 2.10 (3H, s), 2.08 (3H, s), 1.97-1.95 (1H, br. m). T87

δ_(H) 8.09-8.07 (1H, m), 7.68-7.67 (2H, m), 7.46 (1H, t), 6.89 (1H, s), 6.88 (1H, s), 4.89 (1H, d), 4.62 (1H, s), 3.13 (1H, dd), 2.28-2.24 (1H, m), 2.25 (3H, s), 2.10 (3H, s), 2.08 (3H, s), 1.95-1.95 (1H, m). T88

δ_(H) 7.88-7.86 (1H, m), 7.79 (1H, d), 7.55-7.53 (1H, m), 7.39 (1H, t), 6.88 (1H, s), 6.87 (1H, s), 4.87 (1H, d), 4.61 (1H, s), 3.09 (1H, dd), 2.60 (3H, s), 2.25 (3H, s), 2.23-2.20 (1H, m), 2.10 (3H, s), 2.08 (3H, s), 1.96-1.94 (1H, m). T89

δ_(H) 7.62-7.60 (1H, m), 7.56-7.50 (2H, m), 7.39 (1H, t), 6.90 (1H, s), 6.88 (1H, s), 4.88 (1H, br. s), 4.59 (1H, s), 3.05-3.03 (1H, m), 2.26 (3H, s), 2.24- 2.20 (1H, m), 2.10 (3H, s), 2.08 (3H, s), 1.92- 1.89 (1H, m). T90

δ_(H) 8.14 (2H, d), 7.47 (2H, d), 6.89 (1H, s), 6.87 (1H, s), 4.89 (1H, d), 4.63 (1H, s), 3.12 (1H, dd), 2.27-2.23 (1H, m), 2.26 (3H, s), 2.10 (3H, s), 2.08 (3H, s), 1.95-1.91 (1H, m). T91

δ_(H) 7.35-7.31 (2H, m), 7.15-7.12 (2H, m), 6.91 (1H, s), 6.90 (1H, s), 4.87 (1H, br. s), 4.61 (1H, s), 3.07-3.05 (1H, m), 2.27 (3H, s), 2.22-2.20 (1H, m), 2.10 (3H, s), 2.09 (3H, s), 1.93-1.91 (1H, m). T92

δ_(H) 7.54 (2H, d), 7.43-7.41 (2H, m), 6.89 (1H, s), 6.88 (1H, s), 4.87 (1H, d), 4.61 (1H, s), 3.07 (1H, dd), 2.26 (3H, s), 2.23 (1H, dd), 2.10 (3H, s), 2.08 (3H, s), 1.95-1.91 (1H, m). T93

δ_(H) 7.57 (2H, d), 7.41 (2H, d), 6.88 (1H, s), 6.87 (1H, s), 4.86 (1H, d), 4.60 (1H, s), 3.05 (1h, dd), 2.25 (3H, s), 2.23-2.20 (1H, m), 2.09 (3H, s), 2.08 (3H, s), 1.95-1.91 (1H, m). T94

δ_(H) 7.31-7.29 (2H, m), 7.24-7.22 (2H, m), 6.89 (1H, s), 6.88 (1H, s), 4.85 (1H, d), 4.59 (1H, s), 3.00 (1H, dd), 2.26 (3H, s), 2.17 (1H, dd), 2.10 (3H, s), 2.09 (3H, s), 1.99-1.96 (1H, m), 1.30 (9H, s). T95

δ_(H) 7.88 (2H, d), 7.41-7.38 (2H, m), 6.90 (1H, s), 6.88 (1H, s), 4.88 (1H, br. s), 4.63 (1H, s), 3.08 (1H, br. s), 2.58 (3H, s), 2.26 (3H, s), 2.23-2.21 (1H, m), 2.11 (3H, s), 2.09 (3H, s), 1.95-1.93 (1H, m). T96

LC-MS (Method A) ES⁺: MH⁺ = 428; rt = 1.52 mins T97

δ_(H) 6.85 (2H, s), 4.50 (1H, d), 4.37 (1H, d), 3.31- 3.29 (1H, m), 3.12 (1H, d), 2.81 (1H, d), 2.24 (3H, s), 2.14-2.07 (1H, m), 2.05 (3H, s), 2.03 (3H, s), 1.12 (3H, d), 1.07 (1H, dd). T98

δ_(H) 7.33-7.18 (5H, m), 6.84-6.81 (2H, m), 6.35 (1H, d), 6.08 (1H, dd), 4.63 (1H, d), 4.42 (1H, s), 2.68-2.63 (2H, m), 2.55-2.48 (1H, m), 2.22 (3H, s), 2.04 (3H, s), 2.02 (3H, s), 1.85-1.80 (1H, m), 1.64-1.60 (1H, m). T99

δ_(H) 6.90-6.89 (2H, m), 5.80-5.71 (1H, m), 5.05- 4.97 (2H, m), 4.68 (1H, d), 4.44 (1H, s), 2.81- 2.76 (2H, m), 2.51-2.46 (1H, m), 2.26 (3H, s), 2.07 (3H, s), 2.06 (3H, s), 1.89-1.84 (1H, m), 1.67-1.62 (1H, m). T100

δ_(H) 7.27-7.12 (6H, m), 6.83 (2H, br. s), 4.55 (1H, d), 4.33 (1H, s), 2.75-2.71 (2H, m), 2.64 (2H, t), 2.23 (3H, s), 2.04 (6H, s), 1.74-1.68 (3H, m), 1.57-1.50 (1H, m), 1.44-1.41 (1H, m). T101

δ_(H) 6.87 (2H, s), 6.40 (1H, d), 4.95 (1H, s), 4.82 (1H, s), 2.90 (1h, d), 2.81 (1H, d), 2.25 (3H, s), 2.07 (3H, s), 2.03 (3H, s). T102

δ_(H) 6.82 (2H, s), 4.47 (1H, d), 4.25 (1H, s), 2.50- 2.46 (2H, m), 2.22 (3H, s), 2.02 (3H, s), 2.01 (3H, s), 1.69-1.50 (4H, m), 1.34-1.12 (6H, m), 0.88- 0.86 (6H, m). T103

δ_(H) 6.81 (2H, s), 4.47 (1H, d), 4.24 (1H, s), 3.64 (3H, s), 2.52-2.47 (2H, m), 2.28-2.20 (5H, m), 2.00 (6H, s), 1.70-1.48 (H, m), 1.27-1.24 (1H, m). T104

Aproximately 85:15 mixture of E- and Z- isomers. E-isomer: δ_(H) 6.84 (2H, s), 5.42-5.26 (2H, m), 4.53 (1H, d), 4.29 (1H, s), 2.58 (1H, m), 2.37-2.29 (1H, m), 2.23 (3H, s), 2.02 (3H, s), 2.01 (3H, s), 1.86-1.83 (2H, m), 1.75-1.70 (1H, m), 1.63-1.47 (3H, m) ,0.89-0.86 (6H, m). T105

Approximately 3:2 mixture of E- and Z-isomers. E-isomer δ_(H) 6.80 (2H, s), 6.74 (1H, dd), 5.91 (1H, d), 4.58 (1H, d), 4.30 (1H, s), 3.33 (3H, s), 2.85- 2.77 (3H, m), 2.21 (3H, s), 1.97 (3H, s), 194 (3H, s), 1.94-1.91 (1H, m), 1.59-1.54 (1H, m). T106

δ_(H) 6.82 (2H, s), 4.44 (1H, d), 4.24 (1H, s), 2.45- 2.40 (2H, m), 2.22 (3H, s), 2.02 (6H, s), 1.58- 1.52 (2H, m), 1.38-1.33 (1H, m), 1.25-1.16 (2H, m), 0.85-0.82 (3H, m). T107

δ_(H) 6.85 (2H, s), 4.51 (1H, d), 4.43 (1H, d), 3.07 (1H, d), 2.82-2.81 (1H, m), 2.24 (3H, s), 2.10- 2.05 (2H, m), 2.04 (6H, s), 1.87-1.79 (1H, m), 1.53-1.46 (2H, m), 1.00 (3H, t). T108

δ_(H) 8.82 (1H, s), 8.76 (1H, d), 8.03 (1H, dd), 6.82 (2H, s), 4.90 (1H, d), 4.63 (1H, s), 3.55 (1H, dd), 3.16 (1H, d), 3.08 (1H, d), 2.46-2.40 (1H, m), 2.23 (3H, s), 2.08 (6H, s), 2.02-1.96 (1H, m). T109

LC-MS (Method A) ES⁺: MH⁺ = 327; rt = 4.97 mins T110

LC-MS (Method A) ES⁺: MH⁺ = 369; rt = 4.98 mins T111

LC-MS (Method A) ES⁺: MH⁺ = 412; rt = 5.70 mins T112

LC-MS (Method A) ES⁺: MH⁺ = 435; rt = 4.23 mins T113

LC-MS (Method A) ES⁺: MH⁺ = 353; rt = 4.48 mins T114

LC-MS (Method A) ES⁺: MH⁺ = 371; rt = 5.23 mins T115

LC-MS (Method A) ES⁺: MH⁺ = 325; rt = 4.22 mins T116

LC-MS (Method A) ES⁺: MH⁺ = 371; rt = 5.51 mins T117

LC-MS (Method A) ES⁺: MH⁺ = 431; rt = 4.98 mins T118

LC-MS (Method A) ES⁺: MH⁺ = 381; rt = 7.34 mins T119

LC-MS (Method A) ES⁺: MH⁺ = 339, rt = 6.54 mins T120

LC-MS (Method A) ES⁺: MH⁺ = 353; rt = 5.23 mins T121

LC-MS (Method A) ES⁺: MH⁺ = 407; rt = 5.04 mins T122

LC-MS (Method B) ES⁺: MH⁺ = 329; rt = 1.18 mins T123

LC-MS (Method B) ES⁺: MH⁺ = 355; rt = 1.32 mins T124

LC-MS (Method B) ES⁺: MH⁺ = 43; rt = 1.58 mins T125

LC-MS (Method B) ES⁺: MH⁺ = 327; rt = 1.45 mins T126

LC-MS (Method B) ES⁺: MH⁺ = 383; rt = 1.93 mins T127

d₄-MeOH δ_(H) 6.84 (2H, s), 4.50 (2H, s), 3.56 (2H, s), 2.88 (2H, s), 2.23 (3H, s), 2.05 (3H, s), 2.02 (3H, s). T128

d₄-MeOH δ_(H) 8.68 (1H, d), 8.03 (1H, dd), 7.78 (1H, d), 6.89 (2H, s), 4.83 (1H, d), 4.52 (1H, s), 3.36- 3.34 (1H, m), 3.10 (1H, d), 3.03 (1H, d), 2.83 (1H, dd), 2.27 (3H, s), 2.09 (3H, s), 2.08 (3H, s), 1.93- 1.88 (1H, m). T129

d₄-MeOH δ_(H) 8.10 (1H, d), 7.95-7.90 (1H, m), 7.00 (1H, dd), 6.85 (2H, s), 4.77 (1H, d), 4.41 (1H, s), 3.21 (1H, dd), 3.03 (1H, d), 2.96 (1H, d), 2.30 (1H, dd), 2.23 (3H, s), 2.05 (6H, s), 1.85-1.80 (1H, m). T130

d₄-MeOH δ_(H) 8.65 (1H, d), 7.97 (1H, dd), 7.81 (1H, d), 6.85 (2H, s), 4.80 (1H, d), 4.48 (1H, s), 3.34- 3.31 (1H, m), 3.06 (1H, d), 2.99 (1H, d), 2.35 (1H, dd), 2.24 (3H, s), 2.05 (3H, s), 2.04 (3H, s), 1.91- 1.86 (1H, m). T131

d₄-MeOH δ_(H) 8.63 (1H, d), 8.34 (1H, d), 8.22 (1H, dd), 6.92 (2H, s), 4.88 (1H, d), 4.56 (1H, s), 3.48 (1H, dd), 3.14 (1H, d), 3.06 (1H, d), 2.43 (1H, dd), 2.31 (3H, s), 2.12 (3H, s), 2.11 (3H, s), 2.00-1.94 (1H, m). T132

d₄-MeOH δ_(H) 7.39 (1H, dd), 7.18 (1H, d), 7.16 (1H, d), 6.35 (2H, s), 2.79 (2H, s), 2.46 (2H, q), 1.61 (6H, s), 1.07 (3H, t) T133

d₄-MeOH δ_(H) 7.37 (1H, dd), 7.17 (1H, d), 7.14 (1H, d), 6.54 (2H, s), 4.96 (2H, s), 2.79 (2H, s), 2.44 (2H, q), 1.06 (3H, t) T134

d₄-MeOH δ_(H) 7.34 (1H, dd), 7.15 (2H, d), 4.59 (2H, s), 2.78 (2H, s), 2.43 (2H, q), 1.81-1.78 (2H, m), 1.66-1.61 (2H, m), 1.06 (3H, t) T135

d₄-MeOH δ_(H) 8.13 (1H, s), 6.80 (2H, s), 6.76 (1H, d), 5.28 (1H, s), 5.06 (1H, d), 4.11 (3H, s), 2.71 (1H, d), 2.60 (1H, d), 2.21 (3H, s), 2.08 (6H, s). T136

δ_(H) 6.82 (2H, s), 6.48-6.44 (2H, m), 4.98 (1H, s), 2.93-2.87 (2H, m), 2.19 (3H, s), 2.05 (3H, s), 2.02 (3H, s). T137

d₄-MeOH δ_(H) 7.93 (1H, s), 6.82 (1H, s), 6.80 (1H, s), 4.72 (1H, d), 4.71 (1H, d), 4.12 (3H, s), 3.59- 3.54 (1H, m), 2.76 (1H, d), 2.66 (1H, d), 2.41- 2.32 (1H, m), 2.23 (3H, s), 2.10 (3H, s), 2.06 (3H, s), 2.00-1.95 (1H, m). T138

Approximately 9:1 mixture of Isomer A:Isomer B. Isomer A: d₄-MeOH δ_(H) 6.83 (2H, s), 4.77 (1H, d,), 4.69 (1H, d), 3.22 (1H, d), 3.16-3.13 (1H, m), 2.85 (1H, d), 2.35-2.29 (1H, m), 2.23 (3H, s), 2.07 (3H, s), 2.03 (3, s), 1.87 (1H, dd).

T139

d₆-DMSO δ_(H) 7.17 (1H, s), 7.18 (1H, s), 6.50 (2H, s), 4.86 (2H, s) 2.7 (2H, br. s), 2.00 (3H, s), 1.95 (3H, s) T140

d₄-MeOH δ_(H) 6.83 (2H, s), 5.35 (1H, s), 4.64 (1H, d), 4.05-3.93 (4H, m), 2.84-2.80 (2H, m), 2.24 (3H, s), 2.10 (3H, s), 2.08 (3H, s), 1.93-1.85 (2H, m), 1.73-1.68 (1H, m), 1.58-1.54 (1H, m). T141

d₄-MeOH δ_(H) 6.82 (1H, s), 6.80 (1H, s), 5.04 (1H, s), 4.62 (1H, d), 3.66-3.49 (4H, m), 2.72-2.67 (2H, m), 2.23 (3H, s), 2.12 (3H, s), 2.10 (3H, s), 2.11-2.08 (1H, m), 1.94-1.83 (1H, m), 1.70- 1.62 (2H, m), 1.21 (3H, s), 0.74 (3H, s). T142

LC-MS (Method B) ES⁺: MH⁺ = 439; rt = 1.35 mins T143

δ_(H) 7.32 (1H, d), 7.15 (1H, s), 7.02 (1H, d), 6.91- 6.90 (2H, m), 4.75-4.73 (1H, br. m), 4.62 (1H, s), 3.46-3.44 (1H, m), 2.95-2.84 (2H, m), 2.37- 2.28 (10H, m), 2.16-2.11 (1H, m), 1.76-1.73 (1H, m), 1.06-1.02 (6H, m). T144

δ_(H) 7.48 (1H, s), 7.28 (1H, s), 7.13 (1H, d), 6.96- 6.94 (2H, m), 4.86 (1H, s), 4.68 (1H, s), 3.52 (1H, s with fine splitting), 3.11-2.90 (2H, m), 2.40- 2.23 (8H, m), 1.83-1.80 (1H, m), 1.10-1.06 (6H, m). T145

δ_(H) 7.26-7.21 (2H, m), 7.05-7.02 (2H, m), 6.94- 6.88 (3H, m), 4.81 (1H, s), 4.59 (1H, s), 2.99- 2.85 (3H, m), 2.40-2.30 (7H, m), 2.19-2.14 (1H, m), 1.91-1.89 (1H, m), 1.06 (6H, t). T146

δ_(H) 7.08-7.05 (1H, m), 6.97-6.92 (4H, m), 4.80 (1H, br. s), 4.56 (1H, s), 3.10-2.82 (3H, m), 2.38- 2.33 (4H, m), 2.30 (3H, s), 2.23 (3H, s), 2.18- 2.11 (1H, m), 1.90-1.86 (1H, m), 1.08-1.05 (6H, m). T147

δ_(H) 7.16-7.13 (1H, m), 7.08-7.05 (1H, m), 6.96 (1H, s), 6.94 (1H, s), 6.81-6.78 (1H, m), 4.86 (1H, br. s), 4.67 (1H, s), 3.18 (1H, br. s), 3.10 (1H, br. s), 2.85 (1H, br. s), 2.40-2.36 4H, m), 2.31 (3H, s), 2.28 (3H, s), 2.23-2.18 (1H, m), 1.81 (1H, br. s), 1.10-1.06 (6H, m). T148

δ_(H) 7.34-7.31 (1H, m), 7.25-7.15 (3H, m), 6.96 (1H, s), 6.94 (1H, s), 4.87-4.85 (1H, m), 4.65 (1H, s), 3.11-3.08 (1H, m), 3.02-2.98 (1H, m), 2.86-2.80 (1H, m), 2.43-2.33 (4H, m), 2.31 (3H, s), 2.23-2.18 (1H, m), 2.00-1.92 (1H, m), 1.09- 1.06 (6H, m). T149

δ_(H) 7.36 (1H, d), 7.16-7.13 (1H, m), 7.04 (1H, t), 6.95 (1H, s), 6.94 (1H, s), 4.83 (1H, br. s), 4.56 (1H, s), 2.96-2.83 (3H, m), 2.39-2.35 (4H, m), 2.31 (3H, s), 2.21-2.16 (1H, m), 1.88-1.85 (1H, m), 1.08-1.05 (6H, m). T150

δ_(H) 7.41-7.39 (1H, m), 7.35-7.33 (1H, m), 7.12- 7.10 (1H, m), 6.94 (1H, s), 6.93 (1H, s), 4.82- 4.80 (1H, m), 4.56 (1H, s), 2.98-2.80 (3H, m), 2.37-2.33 (4H, m), 2.30 (3H, s), 2.19-2.15 (1H, m), 1.87-1.83 (1H, m), 1.08-1.04 (6H, m). T151

δ_(H) 7.28 (1H, br. s), 7.13-7.11 (1H, m), 7.07-7.05 (1H, m), 6.94 (1H, s), 6.92 (1H, s), 4.79-4.78 (1H, m), 4.55 (1H, s), 2.95-2.80 (3H, m), 2.39- 2.34 (4H, m), 2.33 (3H, s), 2.30 (3H, s), 2.15- 2.10 (1H, m), 1.89-1.84 (1H, m), 1.07-1.04 (6H, m). T152

δ_(H) 7.22-7.18 (3H, m), 6.93 (1H, s), 6.92 (1H, s), 4.79 (1H, s), 4.56 (1H, s), 2.93-2.88 (2H, m), 2.37-2.32 (6H, m), 2.29 (3H, s), 2.13 (1H, br. m), 1.85 (1H, br. m), 1.07-1.04 (6H, m). T153

δ_(H) 7.21-7.18 (1H, m), 6.94 (1H, s), 6.93 (1H, s), 6.90-6.84 (2H, m), 6.76-6.74 (1H, m), 4.81 (1H, br. s), 4.60 (1H, s), 3.80 (3H, s), 2.97-2.83 (2H, m), 2.83-2.35 (5H, m), 2.30 (3H, s), 2.16-2.14 (1H, m), 2.00-1.96 (1H, m), 1.09-1.04 (6H, m). T154

δ_(H) 7.53-7.39 (4H, m), 6.94-6.93 (2H, m), 4.82 (1H, br. s), 4.59 (1H, d), 3.04-3.02 (1H, m), 2.93- 2.89 (2H, br. m), 2.38-2.33 (4H, m), 2.30 (3H, s), 2.18 (3H, s), 2.16 (3H, s), 1.92-1.90 (1H, m), 1.08-1.04 (6H, m). T155

δ_(H) 7.26-7.25 (4H, m), 6.95-6.94 (2H, m), 4.84 (1H, s), 4.60-4.57 (1H, m), 3.09-3.06 (1H, m), 2.99-2.97 (1H, m), 2.85-2.80(1H, m), 2.40- 2.36 (4H, m), 2.31 (3H, s), 2.22-2.17 (1H, m), 1.93-1.89 (1H, m), 1.09-1.05 (6H, m). T156

δ_(H) 7.22-7.20 (2H, m), 6.95-6.93 (2H, m), 6.84- 6.82 (2H, m), 4.83-4.82 (1H, br. m), 4.56 (1H, s), 3.78 (3H, s), 2.98-2.95 (1H, m), 2.90-2.75 (2H, br. s), 2.39-2.35(4H, m), 2.30(3H, s), 2.19- 2.13 (1H, m), 1.95-1.89 (1H, m), 1.09-1.05 (6H, m). T157

δ_(H) 7.57-7.53 (1H, m), 7.44-7.42 (1H, m), 7.09- 7.05 (1H, m), 6.93 (2H, s), 4.84 (1H, br. s), 4.70 (1H, br. s), 3.45-3.33 (1H, m), 3.10-2.90 (2H, m), 2.37-2.32 (4H, m), 2.29 (3H, s), 1.85-1.83 (2H, m), 1.09-1.04 (6H, m). T158

δ_(H) 8.15 (2H, d), 7.46 (2H, dd), 6.95 (1H, s), 6.94 (1H, s), 4.88 (1H, s with fine splitting), 4.62 (1H, s), 4.62 (1H, s), 3.12-3.10 (1H, m), 2.99-2.90 (2H, br. m), 2.40-2.35 (4H, m), 2.31 (3H, s), 2.25- 2.22 (1H, m), 1.93-1.89 (1H, m), 1.08-1.05 (6H, m). T159

δ_(H) 7.31-7.28 (2H, m), 7.13-7.12 (2H, m), 6.94- 6.93 (2H, m), 4.84-4.81 (1H, m), 4.57 (1H, d), 3.00-2.99 (4H, m), 2.98-2.85 (2H, br. m), 2.38- 2.33 (4H, m), 2.30 (3H, s), 2.17-2.14 (1H, m), 1.90-1.87 (1H, m), 1.08-1.04 (6H, m). T160

δ_(H) 7.58 (2H, dd), 7.41-7.40 (2H, m), 6.95 (1H, s), 4.87-4.85 (1H, m), 4.60 (1H, d), 3.06-3.03 (1H, m), 3.04-2.95 (2H, br. m), 2.40-2.33 (4H, m), 2.30 (3H, s), 2.25-2.20 (1H, m), 1.93-1.88 (1H, m), 1.09-1.05 (6H, m). T161

δ_(H) 8.18 (1H, s), 8.10-8.08 (1H, m), 7.69-7.67 (1H, m), 7.48 (1H, t), 6.97 (1H, s), 6.95 (1H, s), 4.91 (1H, d), 4.64 (1H, s), 3.18-3.13 (1H, m), 3.10-2.95 (2H, br. m), 2.40-2.36 (4H, m), 2.31 (3H, s), 1.08 (6H, t). T162

δ_(H) 7.25-7.15 (4H, m), 6.96 (1H, s), 6.94 (1H, s), 4.85 (1H, s), 4.58 (1H, br. s), 3.10-3.05 (1H, br. m), 3.00-2.97 (1H, m), 2.87-2.85 (1H, m), 2.47 (3H, s), 2.42-2.34 (4H, m), 2.31 (3H, s), 2.21- 2.17 (1H, m), 1.96-1.91 (1H, m), 1.00-1.05 (6H, m). T163

δ_(H) 7.42-7.38 (1H, m), 6.94-6.92 (2H, m), 6.85- 6.83 (1H, m), 6.77-6.73 (1H, m), 4.82-4.80 (1H, m), 4.59 (1H, d), 3.38-3.34 (1H, m), 3.05-2.91 (2H, br. m), 2.37-2.34 (4H, m), 2.30 (3H, s), 2.19- 2.15(1H, m), 1.85-1.80 (1H, m), 1.08-1.04 (6H, m). T164

δ_(H) 7.22-7.20 (1H, m), 7.05-7.00 (2H, m), 6.94 (1H, s), 6.92 (1H, s), 4.83 (1H, s), 4.79 (1H, br. s), 3.85-3.82 (1H, m), 3.06-2.89 (2H, br. m), 2.51 (3H, s), 2.39-2.33 (4H, m), 2.30 (3H, s), 2.18- 2.14 (1H, m), 1.99-1.95 (1H, m), 1.05 (6H, t). T165

δ_(H) 7.35 (1H, t), 7.16-7.12 (1H, m), 6.96 (1H, s), 6.61-6.53 (1H, m), 4.86 (1H, br. s), 4.66 (1H, s), 3.17-3.09 (2H, m), 2.87-2.85 (1H, m), 2.42- 2.35 (4H, m), 2.32 (6H, s), 2.26-2.18 (1H, m), 1.83-1.76 (1H, m), 1.08 (6H, t). T166

δ_(H) 7.76-7.74 (3H, m), 6.96 (1H, s), 6.94 (1H, s), 4.89 (1H, br. s), 4.62 (1H, s), 3.15-3.13 (1H, m), 3.12-3.07 (1H, br. m), 2.87 (1H, br. s), 2.43- 2.36 (4H, m), 2.30 (3H, s), 2.28-2.25 (1H, m), 1.92-1.90 (1H, m), 1.09-1.06 (6H, m). T167

δ_(H) 8.26-8.24 (1H, m), 8.10 (1H, dd), 7.71 (1H, d), 6.96 (1H, s), 9.95 (1H, s), 4.89 (1H, br. s), 4.73 (1H, br. s), 3.62 (1H, br. s), 3.13 (1H, br. s), 2.94 (1H, br. s), 2.39-2.33 (4H, m), 2.31 (3H, s), 1.82- 1.80(1H, m), 1.67-1.65 (1H, m), 1.08 (6H, t). T168

δ_(H) 7.58 (1H, s), 7.46 (1H, d), 6.97 (1H, s), 6.95 (1H, s), 4.88 (1H, br. s), 4.64 (1H, s), 3.49-3.47 (1H, m), 3.17-2.86 (2H, br. m), 2.40-2.35 (4H, m), 2.32 (3H, s), 1.81-1.79 (1H, m), .158-1.56 (1H, m), 1.10-1.06 (6H, m). T169

δ_(H) 7.73 (1H, s), 7.48-7.41 (2H, m), 6.96 (1H, s), 6.93 (1H, s), 4.84 (1H, br. s), 4.69 (1H, s), 3.58 (1H, br. s), 3.08-2.93 (2H, br. m), 2.38-2.32 (4H, m), 2.31 (3H, s), 2.27-2.35 (1H, m), 1.84- 1.80 (1H, m), 1.10-1.05 (6H, m). T170

δ_(H) 7.43-7.38 (1H, m), 7.19-7.14 (1H, m), 7.11- 7.07 (1H, m), 7.01-6.96 (1H, m), 6.90-6.89 (2H, m), 4.75 (1H, d), 4.60 (1H, s), 3.35 (1H, dd), 2.90- 2.83 (2H, m), 2.37-2.29 (4H, m), 2.28 (3H, s), 2.12-2.07 (1H, m), 1.84-1.78 (1H, m), 1.06- 1.01 (6H, m). T171

δ_(H) 7.86 (2H, d), 7.34 (2H, d), 6.91-6.90 (2H, m), 4.76 (1H, d), 4.57 (1H, s), 2.97 (1H, dd), 2.87- 2.83 (2H, m), 2.58 (3H, s), 2.42-2.32 (4H, m), 2.28 (3H, s), 2.10-2.02 (1H, m), 1.87-1.82 (1H, m), 1.09-1.05 (6H, m). T172

δ_(H) 7.61 (1H, d), 7.30 (1H, d), 7.12 (1H, dd), 6.94- 6.93 (2H, m), 4.81 (1H, d), 4.67 (1H, s), 3.85 (3H, s), 3.40 (1H, dd), 3.04-2.88 (2H, br. s), 2.40- 2.31 (4H, m), 2.30 (3H, s), 2.29-2.26 (1H, m), 1.89-1.86 (1H, m), 1.06 (6H, t). T173

δ_(H) 6.89 (1H, s), 6.88 (1H, s), 6.78-6.73 (2H, m), 6.67-6.61 (1H, m), 4.66 (1H, d), 4.48 (1H, s), 2.81 (1H, dd), 2.74 (2H, br. s), 2.33-2.27 (4H, m), 2.26 (3H, s), 2.05-1.98 (1H, m), 1.77-1.71 (1H, m), 1.02 (6H, t). T174

δ_(H) 7.78-7.73 (2H, m), 7.44-7.42 (1H, m), 7.35 (1H, t), 6.84 (2H, s), 4.69 (1H, d), 4.50 (1H, s), 2.93 (1H, dd), 2.79-2.76 (2H, m), 2.54 (3H, s), 2.35-2.26 (4H, m), 2.22 (3H, s), 2.05-2.00 (1H, m), 1.82-1.76 (1H, m), 1.04-0.99 (6H, m). T175

δ_(H) 7.95 (2H, d), 7.28 (2H, d), 6.91-6.90 (2H, m), 4.69 (1H, d), 4.53 (1H, s), 4.38 (2H, q), 2.91 (1H, dd), 2.79-2.76 (2H, m), 2.40-2.31 (4H, m), 2.30 (3H, s), 2.03-1.97 (1H, m), 1.83-1.77 (1H, m), 1.43 (2H, t), 1.06 (6H, t). T176

δ_(H) 7.94 (2H, d), 7.33 (2H, d), 6.92-6.91 (2H, m), 4.81 (1H, d), 4.60 (1H, s), 3.89 (3H, s), 3.02 (1H, dd), 2.97-2.80 (2H, br. m), 2.38-2.30 (4H, m), 2.29 (3H, s), 2.16 (1H, dd), 1.93-1.87 (1H, m), 1.07-1.03 (6H, m). T177

δ_(H) 7.78 (1H, dd), 7.71 (1H, dd), 7.59-7.54 (1H, m), 7.37-7.33 (1H, m), 6.91-6.90 (2H, m), 4.79 (1H, d), 4.69 (1H, s), 3.42 (1H, dd), 2.93 (1H, br. s), 2.88-2.86 (1H, m), 2.93-2.30 (4H, m), 2.28 (3H, s), 2.28-2.26 (1H, m), 1.91-1.85 (1H, m), 1.05 (6H, t). T178

δ_(H) 7.05-6.97 (2H, m), 6.87-6.83 (3H, m), 4.62 (1H, d), 4.41 (1H, s), 2.76 (1H, dd), 2.70 (2H, br. s), 2.34-2.24 (5H, m), 2.26 (3H, s), 1.97-1.92 (1H, m), 1.71-1.66 (1H, m), 1.00 (6H, t). T179

δ_(H) 7.15 (1H, t), 7.07 (1H, s), 7.02-7.00 (2H, m), 6.89 (1H, s), 6.88 (1H, s), 4.70 (1H, d), 4.51 (1H, s), 2.85 (1H, dd), 2.80-2.76 (2H, m), 2.37-2.31 (4H, m), 2.32 (3H, s), 2.27 (3H, s), 2.04-1.98 (1H, m), 1.87-1.82 (1H, m), 1.05-1.01 (6H, m). T180

δ_(H) 7.11-7.05 (4H, m), 6.88-6.87 (2H, m), 4.67 (1H, d), 4.47 (1H, s), 2.84 (1H, dd), 2.77-2.73 (2H, m), 2.36-2.28 (4H, m), 2.30 (3H, s), 2.27 (3H, s), 2.01-1.96 (1H, m), 1.84-1.79 (1H, m), 1.05-1.00 (6H, m). T181

δ_(H) 6.90 (1H, s), 6.89 (1H, s), 6.47 (2H, s), 4.70 (1H, d), 4.51 (1H, s), 3.84 (6H, s), 3.80 (3H, s), 2.84-2.79 (3H, m), 2.37-2.30 (4H, m), 2.28 (3H, s), 2.07-2.02 (1H, m), 1.86-1.80 (1H, m), 1.07- 1.02 (6H, m). T182

δ_(H) 7.53 (1H, s), 7.49-7.43 (2H, m), 7.38-7.34 (1H, m), 6.89 (1H, s), 6.88 (1H, s), 4.71 (1H, d), 4.47 (1H, s), 289 (1H, dd), 2.82-2.78 (2H, m), 2.36-2.26 (4H, m), 2.25 (3H, s), 2.05 (1H, dd), 1.78-1.72 (1H, m), 1.02 (6H, t) T183

δ_(H) 7.79 (1H, d), 7.74-7.72 (1H, m), 7.69-7.66 (1H, m), 6.96 (1H, s), 6.95 (1H, s), 4.90 (1H, d), 4.60 (1H, s), 3.11 (1H, dd), 2.99 (2H, br. s), 2.40- 2.32 (4H, m), 2.30 (3H, s), 2.29-2.26 (1H, m), 1.90-1.84 (1H, m), 1.09-1.05 (6H, m). T184

δ_(H) 8.29 (1H, d), 7.97 (1H, dd), 7.29 (1H, d), 6.97 (1H, s), 6.95 (1H, s), 4.92 (1H, d), 4.72 (1H, s), 3.26 (1H, dd), 3.03 (2H, br. s), 2.43 (3H, s), 2.40- 2.33 (4H, m), 2.32 (3H, s), 2.26 (1H, dd), 1.87- 1.85 (1H, m), 1.12-1.06 (6H, m). T185

δ_(H) 7.19-7.16 (2H, m), 6.97-6.90 (4H, m), 4.71 (1H, d), 4.48 (1H, s), 2.88 (1H, dd), 2.82-2.78 (2H, m), 2.37-2.30 (4H, m), 2.28 (3H, s), 2.05 (1H, dd), 1.83-1.77 (1H, m), 1.05-1.01 (6H, m). T186

d₄-MeOH δ_(H) 6.82 (1H, s), 6.80 (1H, s), 4.87 (1H, d), 4.77 (1H, d), 4.63 (1H, d), 2.72 (1H, d), 2.65 (1H, d), 2.23 (3H, s), 2.12 (3H, s), 2.08 (3H, s), 2.07-2.03 (1H, m), 1.95-1.86 (1H, m), 1.76- 1.70 (1H, m), 1.62-1.55 (1H, m). T187

d₄-MeOH δ_(H) 8.65 (1H, s), 8.54 (1H, br. s), 8.46 (1H, br. s), 6.87 (2H, s), 4.82 (1H, d), 4.72 (1H, s), 3.48-3.46 (1H, m), 3.13 (1H, d), 3.04 (1H, d), 2.25 (3H, s), 2.25-2.18 (2H, m), 2.09 (3H, s), 2.07 (3H, s), 1.79-1.74 (1H, m), 1.72-1.67 (1H, m). T188

d₄-MeOH δ_(H) 8.93 (1H, s, 8.09-8.06 (2H, m), 7.85-7.78 (2H, m), 6.87 (2H, s), 4.90 (1H, s), 4.87 (1H, d), 3.66 (1H, dd), 3.19 (1H, d), 3.09 (1H, d), 2.44-2.33 (2H, m), 2.25 (3H, s), 2.09 (3H, s), 2.08 (3H, s). T189

d₄-MeOH δ_(H) 7.23 (2H, s), 4.61 (2H, t), 2.88 (2H, s), 2.09 (6H, s), 1.83 (2H, m), 1.69 (2H, m) T190

d₄-MeOH δ_(H) 7.14-7.04 (3H, m), 4.61 (2H, t), 2.88 (2H, s), 2.11 (6H, s), 1.83 (2H, m), 1.69 (2H, m) T191

d₄-MeOH δ_(H) 7.36 (1H, dd), 7.17 (1H, d), 7.15 (1H, d), 2.81 (2H, s), 2.48-2.43 (2H, m), 1.84-1.79 (2H, m), 1.69-1.65 (2H, m), 1.51 (6H, s), 1.08 (3H, t). T192

d₄-MeOH δ_(H) 6.94 (1H, d), 6.78 (1H, d), 6.73 (1H, dd), 4.59 (2H, s), 3.77 (3H, s), 2.82 (2H, s), 2.10 (3H, s), 1.84-1.79 (2H, m), 1.69-1.62 (2H, m). T193

d₄-MeOH δ_(H) 7.84 (1H, br. s), 6.78 (2H, s), 4.89 (1H, br. s), 4.84 (1H, s), 3.28 (1H, br. s), 3.02 (1H, br. s), 2.94 (1H, br. s), 2.57-2.46 (2H, m), 2.53 (3H, s), 2.18 (3H, s), 2.05 (3H, s), 2.03 (3H, s), 2.02 (3H, s). T194

d₄-MeOH δ_(H) 8.09-8.06 (1H, m), 8.00-7.98 (1H, m), 7.73-7.70 (2H, m), 6.86 (2H, s), 4.99 (1H, s), 4.80 (1H, d), 3.19-3.10 (3H, m), 2.49-2.43 (1H, m), 2.34-2.28 (1H, m), 2.25 (3H, s), 2.07 (3H, s), 2.06 (3H, s), 1.46 (3H, t). T195

d₄-MeOH δ_(H) 7.04 (1H, br. s), 6.86 (2H, s), 5.93 (1H, br. s), 4.86 (1H, br. s), 4.78 (1H, s), 3.18 (1H, br. s), 3.02 (1H, br. s), 2.94 (1H, br. s), 2.59 (3H, s), 2.37 (3H, s), 2.24 (3H, s), 2.16 (3H, s), 2.07 (6H, m). T196

d₄-MeOH δ_(H) 8.79 (1H, s), 8.59 (1H, s), 6.87 (1H, s), 4.95 (1H, s), 4.92 (1H, d), 3.74-3.71 (1H, m), 2.87 (2H, m), 2.26 (2H, m), 2.18 (3H, s), 2.10 (3H, s), 2.07 (3H, s). T197

d₄-MeOH δ_(H) 7.45-7.42 (3H, m), 7.29-7.23 (2H, m), 7.17-7.15 (2H, m), 6.80 (2H, s), 4.82 (1H, br. s), 4.73 (1H, br. s), 3.21 (1H, br. s), 2.90 (1H, br. s), 2.84 (1H, br. s), 2.20 (3H s), 2.09-2.07 (2H, m), 2.05 (6H, s). T198

d₄-MeOH δ_(H) 8.78 (1H, br. s), 7.96 (1H, br. s), 6.84 (3H, s), 4.82 (2H, br. s), 3.51 (1H, br. s), 2.98 (1H, br. s), 2.90 (1H, br. s), 2.35 (1H, br. s), 2.22 (3H, s), 2.04-2.02 (7H, m). T199

d₄-MeOH δ_(H) 7.81 (1H, s), 7.26 (1H, s), 6.92 (1H, s), 6.90 (1H, s), 4.91 (1H, d), 4.64 (1H, s), 3.19- 3.17 (1H, m), 2.99-2.95 (2H, m), 2.32-2.27 (1H, m), 2.26 (3H, s), 2.09 (3H, s), 2.07 (3H, s), 1.93- 1.90 (1H, m). T200

d₄-MeOH δ_(H) 7.95 (1H, br. s), 7.86 (1H, br. s), 7.44 (1H, br. s), 6.88 (1H, s), 6.84 (1H, s), 4.86 (1H, br. s), 4.71 (1H, br. s), 3.44-3.40 (1H, br. s), 3.07 (1H, br. s), 2.85 (1H, br. s), 2.22 (3H, s), 2.15- 2.11 (2H, m), 2.10 (3H, s), 2.05 (3H, s). T201

d₄-MeOH δ_(H) 7.79 (1H, t), 7.53 (2H, d), 6.86 (2H, s), 4.78 (1H, s), 4.71 (1H, s), 3.35-3.31 (1H, m), 2.88 (1H, br. s), 2.79 (1H, br. s), 2.22 (3H, s), 2.17- 2.09(2H, m), 2.04 (3H, s), 2.02 (3H, s). T202

d₄-MeOH δ_(H) 8.76 (1H, br. s), 8.61 (1H, d), 8.32 (1H, d), 7.96 (1H, d), 7.85 (1H, d), 6.86 (2H, s), 4.84 (1H, s), 4.11 (1H, dd), 3.24 (1H, d), 3.13 (1H, d), 2.58-2.54 (1H, m), 2.24 (3H, s), 2.07 (6H, s), 1.95-1.91 (1H, m). T203

d₄-MeOH δ_(H) 9.07 (1H, s), 8.38 (1H, s), 6.87 (2H, s), 4.77 (1H, s), 3.77-3.74 (1H, m), 3.04 (2H, br. s), 2.40-2.37 (1H, m), 2.29-2.25 (1H, m), 2.25 (3H, s), 2.06 (3H, s), 2.04 (3H, s). T204

d₄-MeOH δ_(H) 6.85 (2H, s), 6.72 (1H, d), 5.03 (1H, d), 3.96 (1H, s), 2.92-2.88 (2H, m), 2.24 (3H, s), 2.06 (3H, s), 2.01 (3H, s). T205

d₆-DMSO δ_(H) 11.92 (1H, s), 7.05 (1H, d), 6.96 (1H, d), 6.77 (1H, s), 4.50 (2H, s), 2.74 (2H, br. s), 2.23 (3H, s), 2.03 (3H, s), 1.71-1.65 (2H, m), 1.57-1.53 (2H, m). T206

d₆-DMSO δ_(H) 12.21 (1H, s), 7.20 (1H, dd), 6.99 (1H, td), 6.75 (1H, dd), 4.51 (2H, s), 2.76 (2H, br. s), 2.04 (3H, s), 1.71-1.65 (2H, m), 1.60-1.52 (2H, m). T207

d₆-DMSO δ_(H) 12.27 (1H, s), 7.21 (2H, s), 6.97 (1H, s), 4.51 (2H, s), 2.78 (2H, br. s), 2.05 (3H, s), 1.73-1.63 (2H, m), 1.60-1.51 (2H, m). T208

d₄-MeOH δ_(H) 6.61 (2H, s), 4.64-4.50 (2H, m), 3.74 (3H, s), 2.83 (2H, s), 2.04 (6H, d), 1.87-1.77 (2H, m), 1.70-1.59 (2H, m). T209

d₄-MeOH δ_(H) 8.30 (1H, s), 6.86 (2H, s), 4.89 (1H, s), 4.73 (1H, d), 3.47 (1H, dd), 3.09 (1H, d), 3.04 (1H, d), 2.55 (3H, s), 2.39-2.35 (1H, m), 2.30 (3H, s), 2.25 (3H, s), 2.17 (1H, dd), 2.06 (3H, s), 2.04 (3H, s). T210

d₄-MeOH δ_(H) 8.72 (1H, d), 7.72 (1H, s), 7.58 (1H, d), 6.86 (2H, s), 4.81 (1H, d), 4.68 (1H, s), 3.51 (1H, dd), 3.10 (1H, d), 3.03 (1H, d), 2.33 (1H, dd), 2.25 (3H, s), 2.16-2.11 (1H, m), 2.06 (3H, s), 2.05 (3H, s). T211

d₄-MeOH δ_(H) 7.21-7.19 (1H, m), 6.92-6.90 (2H, m), 6.86 (2H, s), 4.72 (1H, d), 4.43 (1H, s), 3.49 (1H, dd), 3.02 (1H, d), 2.93 (1H, d), 2.29 (1H, dd), 2.25 (3H, s), 2.05 (6H, s), 1.98-1.93 (1H, m). T212

d₄-MeOH δ_(H) 7.41 (1H, d), 7.29 (1H, dd), 7.19 (1H, d), 4.65-4.60 (2H, m), 2.87 (2H, s), 1.86-1.79 (2H, m), 1.70-1.63 (2H, m). T213

d₄-MeOH δ_(H) 7.44-7.41 (2H, m), 7.08 (2H, t), 6.88 (1H, s), 6.87 (1H, s), 4.89(1H, s), 4.73 (1H, s), 3.68 (1H, d), 3.59 (1H, d), 3.10-3.06 (2H, m), 2.25 (3H, s), 2.07 (3H, s), 2.5 (3H, s). T214

d₄-MeOH δ_(H) 8.24 (2H, d), 7.66 (2H, d), 6.88 (2H, s), 4.93 (1H, s), 4.68 (1H, s), 3.76 (2H, s), 3.13- 3.11 (2H, m), 2.25 (3H, s), 2.07 (3H, s), 2.05 (3H, s). T215

d₄-MeOH δ_(H) 7.34-7.30 (1H, m), 7.25-7.18 (2H, m), 6.89 (1H, s), 6.87 (1H, s), 4.90 (1H, s), 4.75 (1H, s), 3.67 (1H, d), 3.58 (1H, d), 3.10-3.05 (2H, m), 2.26 (3H, s), 2.07 (3H, s), 2.05 (3H, s). T216

d₄-MeOH δ_(H) 8.53 (1H, s), 7.83 (1H, d), 7.64 (1H, d), 6.91 (2H, s), 3.12 (1H, dd), 2.97 (2H, br. s), 2.47 (1H, dd), 2.27 (3H, s), 1.84-1.79 (1H, m), 2.11 (3H, s), 2.08 (3H, s), 1.71 (3H, s), 1.10 (3H, s). T217

d₄-MeOH δ_(H) 7.92 (1H, d), 7.77-7.73 (1H, m), 6.91-6.88(3H, m), 3.04 (1H, dd), 2.96-2.92 (2H, m), 2.43(1H, dd), 2.25 (3H, s), 2.11 (3H, s), 2.08 (3H, s), 1.76 (1H, dd), 1.70 (3H, s), 1.09 (3H, s). T218

d₄-MeOH δ_(H) 7.41 (1H, d), 6.88 (2H, s), 6.35-6.34 (1H, m), 6.14 (1H, d), 4.72 (1H, d), 4.59 (1H, s), 3.26(1H, dd), 3.02 (1H, d), 2.94 (1H, d), 2.27 (3H, s), 2.18-2.12 (1H, m), 2.08 (3H, s), 2.06 (3H, s), 2.05-2.01 (1H, m). T219

d₄-MeOH δ_(H) 7.60 (1H, d), 7.06 (1H, d), 6.89 (2H, s), 4.79 (1H, d), 4.47 (1H, s), 3.63 (1H, dd), 3.06 (1H, d), 3.00 (1H, d), 2.36 (1H, dd), 2.27 (3H, s), 2.07 (6H, s), 1.97-1.91 (1H, m). T220

δ_(H) 7.39 (1H, dd), 7.27-7.33 (1H, m), 6.97 (1H, dd), 4.68 (2H, m), 2.74 (2H, br. s), 2.48 (2H, q), 1.78- 1.87 (2H, m), 1.56 (2H, m), 1.11 (3H, t). T221

δ_(H) 7.05-6.99 (1H, m), 4.76-4.67 (2H, m), 2.84 (2H, br. s), 2.38 (3H, s), 2.24 (3H, d), 2.05 (3H, d), 1.88-1.85 (2H, m), 1.64-1.58 (2H, m). T222

d₄-MeOH δ_(H) 8.11 (2H, dd), 8.61 (2H, t), 6.86 (2H, s), 4.81 (1H, s), 4.67 (1H, d), 3.81 (1H, dd), 3.14 (1H, d), 3.03 (1H, d), 2.24 (3H, s), 2.23-2.19 (1H, m), 2.11-2.09 (1H, m), 2.06 (3H, s), 2.02 (3H, s). T223

d₄-MeOH δ_(H) 7.39-7.36 (2H, m), 6.98-6.94 (2H, m), 6.88 (1H, s), 6.86 (1H, s), 4.95 (1H, s), 4.53 (1H, s), 3.63 (1H, d), 3.08 (1H, d), 3.03 (1H, d), 2.88-2.86 (1H, m), 2.25 (3H, s), 2.09 (3H, s), 2.06 (3H, s). T224

d₄-MeOH δ_(H) 7.81-7.76 (1H, m), 7.73-7.70 (1H, m), 7.29-7.23 (1H, m), 6.88 (2H, s), 4.96 (1H, s), 4.79 (1H, d), 3.47 (1H, dd), 3.04-2.92 (2H, m), 2.25 (3H, s), 2.11-2.07(1H, m), 2.07 (3H, s), 2.04 (3H, s), 1.96-1.88 (1H, m). T225

d₄-MeOH δ_(H) 7.16-7.12 (1H, m), 7.01-6.90 (2H, m), 6.78 (1H, s), 6.76 (1H, s), 4.94 (1H, s), 4.54 (1H, s), 3.39 (1H, d), 3.12 (1H, d), 2.28-2.80 (2H, br. m), 2.14 (3H, s), 2.00 (3H, s), 1.96 (3H, s). T226

d₄-MeOH δ_(H) 7.43 (1H, s), 7.38 (1H, s), 6.88 (2H, s), 6.42 (1H, d), 4.93 (1H, s), 4.71 (1H, d), 3.09 (1H, dd), 2.99 (1H, d), 2.93 (1H, d), 2.27 (3H, s), 2.17 (1H, dd), 2.08 (6H, m), 1.85-1.80 (1H, m). T227

δ_(H) 7.92-7.81 (3H, m), 7.42-7.29 (2H, m), 6.85 (2H, s), 4.78 (1H, d), 4.59 (1H, s), 3.57 (1H, dd), 3.14 (1H, d), 3.00 (1H, d), 2.31 (1H, dd), 2.24 (3H, s), 2.07 (3H, s), 2.05 (3H, s), 2.04-1.98 (1H, m). T228

δ_(H) 6.86 (2H, s), 6.47 (2H, s), 5.01 (2H, s), 2.74 (2H, s), 2.23 (3H, s), 2.08 (3H, s), 2.06 (3H, s). T229

δ_(H) 6.65 (2H, s), 6.26 (1H, s), 4.75 (1H, s), 4.67 (1H, s), 2.62 (1H, d), 2.52 (1H, d), 2.03 (3H, s), 1.84 (3H, s), 1.80 (3H, s), 0.00 (9H, s).

The compounds of the following Tables 1 to 146 can be obtained in an analogous manner.

Table 1 covers compounds of formula (A)

wherein R¹, R² and R⁴ are methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

TABLE 1 R⁶ R⁷ R⁸ R⁹ R¹⁰ R¹¹ 1.001 H H H H H H 1.002 H H H H H CH₃ 1.003 H H H H H CH₂OH 1.004 H H H H H CH₂OCH₃ 1.005 H H H H H CH₂OCH₂CH₃ 1.006 H H H H H CH₂OCH₂OCH₃ 1.007 H H H H H CH₂OCH₂OCH₂CH₃ 1.007 H H H H H CH₂OCH₂CO₂CH₃ 1.008 H H H H H CH₂OCH₂CO₂CH₂CH₃ 1.009 H H H H H CH₂OCH₂CN 1.010 H H H H H CH(OH)CH₃ 1.011 H H H H H CH(CH₃)OCH₃ 1.012 H H H H H CH(CH₃)OCH₂CH₃ 1.013 H H H H H CHO 1.014 H H H H H COCH₃ 1.015 H H H H H CH₂COCH₃ 1.016 H H H H H CH₂CH₂COCH₃ 1.017 H H H H H CO₂H 1.018 H H H H H CO₂CH₃ 1.019 H H H H H CO₂CH₂CH₃ 1.020 H H H H H CH₂CO₂CH₃ 1.021 H H H H H CH₂CO₂CH₂CH₃ 1.022 H H H H H CH₂CH₂CO₂CH₃ 1.023 H H H H H CH₂CH₂CO₂CH₂CH₃ 1.024 H H H H H CONH₂ 1.025 H H H H H CONHCH₃ 1.026 H H H H H CONHCH₂CH₃ 1.027 H H H H H CON(CH₃)₂ 1.030 H H H H H CON(CH₂CH₃)₂ 1.031 H H H H H CON(CH₃)OCH₃ 1.032 H H H H H CH═NOH 1.033 H H H H H CH═NOCH₃ 1.034 H H H H H CH═NOCH₂CH₃ 1.035 H H H H H C(CH₃)═NOH 1.036 H H H H H C(CH₃)═NOCH₃ 1.037 H H H H H CH₂OC(O)CH₃ 1.038 H H H H H CH₂OC(O)CH₂CH₃ 1.039 H H H H H CH₂OC(O)CH(CH₃)₂ 1.040 H H H H H CH₂OC(O)C(CH₃)₃ 1.039 H H H H H CH₂OC(O)NHCH₃ 1.040 H H H H H CH₂OC(O)NHCH₂CH₃ 1.041 H H H H H CH₂OC(O)NHCH₂CH₂CH₃ 1.042 H H H H H CH₂OC(O)NHC(CH₃)₃ 1.043 H H H H H CH₂NH₂ 1.044 H H H H H CH₂NHCHO 1.045 H H H H H CH₂NHC(O)CH₃ 1.046 H H H H H CH₂NHC(O)OCH₃ 1.047 H H H H H NHCO₂CH₃ 1.048 H H H H H NHCO₂C(CH₃)₃ 1.049 H H H H H CN 1.050 H H H H H CH₂SCH₃ 1.051 H H H H H CH₂SCH₂CH₃ 1.052 H H H H H CH₂SCH₂CH₂CH₃ 1.053 H H H H H CH₂SCH(CH₃)₂ 1.054 H H H H H CH₂S(O)CH₃ 1.055 H H H H H CH₂SO₂CH₃ 1.056 H H H H H CH₂SCH₂CH₃ 1.057 H H H H H CH₂S(O)CH₂CH₃ 1.058 H H H H H CH₂SO₂CH₂CH₃ 1.059 H H H H H OCH₃ 1.060 H H H H H OCH₂CH₃ 1.061 H H H H H CH(OCH₃)₂ 1.062 H H H H H CH(OCH₂CH₃)₂ 1.063 H H H H H 1,3-dioxolan-2-yl 1.064 11 H H H H 1,3-dioxan-2-yl 1.065 H H H H H 5,5-dimethyl-1,3-dioxan- 2-yl 1.066 H H H H H CH₂CH₃ 1.067 H H H H H n-propyl 1.068 H H H H H isopropyl 1.069 H H H H H n-butyl 1.070 H H H H H isobutyl 1.071 H H H H H sec-butyl 1.072 H H H H H tert-butyl 1.073 H H H H H n-pentyl 1.074 H H H H H neopentyl 1.075 H H H H H n-hexyl 1.076 H H H H H n-heptyl 1.077 H H H H H CH₂CN 1.078 H H H H H cyclopropyl 1.079 H H H H H cyclobutyl 1.080 H H H H H cyclopentyl 1.081 H H H H H cyclohexyl 1.082 H H H H H CH₂-cyclopropyl 1.083 H H H H H benzyl 1.084 H H H H H CH₂CF₃ 1.085 H H H H H CH₂F 1.086 H H H H H CHF₂ 1.087 H H H H H CF₃ 1.088 H H H H CH₃ H 1.089 H H H H CH₂CH₃ H 1.090 H H H H n-propyl H 1.091 H H H H isopropyl H 1.092 H H H H n-butyl H 1.093 H H H H isobutyl H 1.094 H H H H sec-butyl H 1.095 H H H H tert-butyl H 1.096 H H H H vinyl H 1.097 H H H H ethynyl H 1.098 H H H H trimethylsilylethynyl H 1.099 H H H H CH₂OH H 1.100 H H H H CH₂OCH₃ H 1.101 H H H H CH₂OCH₂CH₃ H 1.102 H H H H CH₂OCH₂OCH₃ H 1.103 H H H H CH₂OCH₂OCH₂CH₃ H 1.104 H H 11 H CH₂OCH₂CH₂OCH₃ H 1.105 H H H H CHO H 1.106 H H H H COCH₃ H 1.107 H H H H CO₂H H 1.108 H H H H CO₂CH₃ H 1.109 H H H H CO₂CH₂CH₃ H 1.110 H H H H CONH₂ H 1.111 H H H H CONHCH₃ H 1.112 H H H H CONHCH₂CH₃ H 1.113 H H H H CON(CH₃)₂ H 1.114 H H H H CON(CH₂—CH₃)₂ H 1.115 H H H H CON(CH₃)OCH₃ H 1.116 H H H H CH═NOH H 1.117 H H H H CH═N—OCH₃ H 1.118 H H H H CH═N—OCH₂CH₃ H 1.119 H H H H C(CH₃)═N—OH H 1.120 H H H H C(CH₃)═N—OCH₃ H 1.121 H H H H CH₂OC(O)—NHCH₃ H 1.122 H H H H CH₂NH₂ H 1.123 H H H H CH₂NHCHO H 1.124 H H H H CH₂NHC(O)CH₃ H 1.125 H H H H CH₂NHC(O)OCH₃ H 1.126 H H H H NHCO₂CH₃ H 1.127 H H H H NHCO₂C(CH₃)₃ H 1.128 H H H H CH(OH)CH₃ H 1.129 H H H H CH(CH₃)OCH₃ H 1.130 H H H H CN H 1.131 H H H H CH₂SCH₃ H 1.132 H H H H CH₂S(O)CH₃ H 1.133 H H H H CH₂SO₂CH₃ H 1.134 H H H H CH₂SCH₂CH₃ H 1.135 H H H H CH₂S(O)CH₂CH₃ H 1.136 H H H H CH₂SO₂CH₂CH₃ H 1.137 H H H H OCH₃ H 1.138 H H H H OCH₂CH₃ H 1.139 H H H H CH(OCH₃)₂ H 1.140 H H H H CH(OCH₂CH₃)₂ H 1.141 H H H H cyclopropyl H 1.142 H H H H cyclobutyl H 1.143 H H H H cyclopentyl H 1.144 H H H H cyclohexyl H 1.145 H H H H F H 1.146 H H H H Cl H 1.147 H H H H Br H 1.148 H H H H I H 1.149 H H H H OH H 1.150 H H H H phenyl H 1.151 H H H H 2-acetylphenyl H 1.152 H H H H 3-acetylphenyl H 1.153 H H H H 4-acetylphenyl H 1.154 H H H H 2-chlorophenyl H 1.155 H H H H 3-chlorophenyl H 1.156 H H H H 4-chlorophenyl H 1.157 H H H H 2-cyanophenyl H 1.158 H H H H 3-cyanophenyl H 1.159 H H H H 4-cyanophenyl H 1.160 H H H H 2-fluorophenyl H 1.161 H H H H 3-fluorophenyl H 1.162 H H H H 4-fluorophenyl H 1.163 H H H H 2-methoxyphenyl H 1.164 H H H H 3-methoxyphenyl H 1.165 H H H H 4-methoxyphenyl H 1.166 H H H H 2-methylphenyl H 1.167 H H H H 3-methylphenyl H 1.168 H H H H 4-methylphenyl H 1.169 H H H H 2-nitrophenyl H 1.170 H H H H 3-nitrophenyl H 1.171 H H H H 4-nitrophenyl H 1.172 H H H H 2-thiomethylphenyl H 1.173 H H H H 3-thiomethylphenyl H 1.174 H H H H 4-thiomethylphenyl H 1.175 H H H H 2-trifluoromethoxyphenyl H 1.176 H H H H 3-trifluoromethoxyphenyl H 1.177 H H H H 4-trifluoromethoxyphenyl H 1.178 H H H H 2-trifluoromethylphenyl H 1.179 H H H H 3-trifluoromethylphenyl H 1.180 H H H H 4-trifluoromethylphenyl H 1.181 H H H H 2,3-dichlorophenyl H 1.182 H H H H 2,4-dichlorophenyl H 1.183 H H H H 2,5-dichlorophenyl H 1.184 H H H H 2,6-dichlorophenyl H 1.185 H H H H 3,4-dichlorophenyl H 1.186 H H H H 3,5-dichlorophenyl H 1.187 H H H H 2,3-difluorophenyl H 1.188 H H H H 2,4-difluorophenyl H 1.189 H H H H 2,5-difluorophenyl H 1.190 H H H H 2,6-difluorophenyl H 1.191 H H H H 3,4-difluorophenyl H 1.192 H H H H 3,5-difluorophenyl H 1.193 H H H H 2,4,6-trifluorophenyl H 1.194 H H H H 2,4-dimethylphenyl H 1.195 H H H H 2,4,6-trimethylphenyl H 1.196 H H H H 3,4,5-trimethoxyphenyl h 1.197 H H H H 2-chloro-3-cyanophenyl H 1.198 H H H H 2-chloro-4-cyanophenyl H 1.199 H H H H 2-chloro-5-cyanophenyl H 1.200 H H H H 2-chloro-6-cyanophenyl H 1.201 H H H H 3-chloro-2-cyanophenyl H 1.202 H H H H 3-chloro-4-cyanophenyl H 1.203 H H H H 3-chloro-5-cyanophenyl H 1.204 H H H H 5-chloro-2-cyanophenyl H 1.205 H H H H 4-chloro-2-cyanophenyl H 1.206 H H H H 4-chloro-3-cyanophenyl H 1.207 H H H H 2-chloro-3-fluorophenyl H 1.208 H H H H 2-chloro-4-fluorophenyl H 1.209 H H H H 2-chloro-5-fluorophenyl H 1.210 H H H H 2-chloro-6-fluorophenyl H 1.211 H H H H 3-chloro-2-fluorophenyl H 1.212 H H H H 3-chloro-4-fluorophenyl H 1.213 H H H H 3-chloro-5-fluorophenyl H 1.214 H H H H 5-chloro-2-fluorophenyl H 1.215 H H H H 4-chloro-2-fluorophenyl H 1.216 H H H H 4-chloro-3-fluorophenyl H 1.217 H H H H 2-chloro-3-methylphenyl H 1.218 H H H H 2-chloro-4-methylphenyl H 1.219 H H H H 2-chloro-5-methylphenyl H 1.220 H H H H 2-chloro-6-methylphenyl H 1.221 H H H H 3-chloro-2-methylphenyl H 1.222 H H H H 3-chloro-4-methylphenyl H 1.223 H H H H 3-chloro-5-methylphenyl H 1.224 H H H H 5-chloro-2-methylphenyl H 1.225 H H H H 4-chloro-2-methylphenyl H 1.226 H H H H 4-chloro-3-methylphenyl H 1.227 H H H H 2-cyano-3-fluorophenyl H 1.228 H H H H 2-cyano-4-fluorophenyl H 1.229 H H H H 2-cyano-5-fluorophenyl H 1.230 H H H H 2-cyano-6-fluorophenyl H 1.231 H H H H 3-cyano-2-fluorophenyl H 1.232 H H H H 3-cyano-4-fluorophenyl H 1.233 H H H H 3-cyano-5-fluorophenyl H 1.234 H H H H 5-cyano-2-fluorophenyl H 1.235 H H H H 4-cyano-2-fluorophenyl H 1.236 H H H H 4-cyano-3-fluorophenyl H 1.237 H H H H 2-fluoro-3-methylphenyl H 1.238 H H H H 2-fluoro-4-methylphenyl H 1.239 H H H H 2-fluoro-5-methylphenyl H 1.240 H H H H 2-fluoro-6-methylphenyl H 1.241 H H H H 3-fluoro-2-methylphenyl H 1.242 H H H H 3-fluoro-4-methylphenyl H 1.243 H H H H 3-fluoro-5-methylphenyl H 1.244 H H H H 5-fluoro-2-methylphenyl H 1.245 H H H H 4-fluoro-2-methylphenyl H 1.246 H H H H 4-fluoro-3-methylphenyl H 1.247 H H H H pyridin-2-yl H 1.248 H H H H pyridin-3-yl H 1.249 H H H H pyridin-4-yl H 1.250 H H H H 3-chloropyridin-2-yl H 1.251 H H H H 4-chloropyridin-2-yl H 1.252 H H H H 5-chloropyridin-2-yl H 1.253 H H H H 6-chloropyridin-2-yl H 1.254 H H H H 2-chloropyridin-3-yl H 1.255 H H H H 4-chloropyridin-3-yl H 1.256 H H H H 5-chloropyridin-3-yl H 1.257 H H H H 2-chloropyridin-4-yl H 1.258 H H H H 3-chloropyridin-4-yl H 1.259 H H H H 2-chloropyridin-5-yl H 1.260 H H H H 3-cyanopyridin-2-yl H 1.261 H H H H 4-cyanopyridin-2-yl H 1.262 H H H H 5-cyanopyridin-2-yl H 1.263 H H H H 6-cyanopyridin-2-yl H 1.264 H H H H 2-cyanopyridin-3-yl H 1.265 H H H H 4-cyanopyridin-3-yl H 1.266 H H H H 5-cyanopyridin-3-yl H 1.267 H H H H 2-cyanopyridin-5-yl H 1.268 H H H H 3-fluoropyridin-2-yl H 1.269 H H H H 4-fluoropyridin-2-yl H 1.270 H H H H 5-fluoropyridin-2-yl H 1.271 H H H H 6-fluoropyridin-2-yl H 1.272 H H H H 2-fluoropyridin-3-yl H 1.273 H H H H 4-fluoropyridin-3-yl H 1.274 H H H H 5-fluoropyridin-3-yl H 1.275 H H H H 2-fluoropyridin-5-yl H 1.276 H H H H 3-nitropyridin-2-yl H 1.277 H H H H 4-nitropyridin-2-yl H 1.278 H H H H 5-nitropyridin-2-yl H 1.279 H H H H 6-nitropyridin-2-yl H 1.280 H H H H 2-nitropyridin-3-yl H 1.281 H H H H 4-nitropyridin-3-yl H 1.282 H H H H 5-nitropyridin-3-yl H 1.283 H H H H 2-nitropyridin-5-yl H 1.284 H H H H 3-trifluoromethylpyridin-2-yl H 1.285 H H H H 4-trifluoromethylpyridin-2-yl H 1.286 H H H H 5-trifluoromethylpyridin-2-yl H 1.287 H H H H 6-trifluoromethylpyridin-2-yl H 1.288 H H H H 2-trifluoromethylpyridin-3-yl H 1.289 H H H H 4-trifluoromethylpyridin-3-yl H 1.290 H H H H 5-trifluoromethylpyridin-3-yl H 1.291 H H H H 2-trifluoromethylpyridin-5-yl H 1.292 H H H H 2,6-bis(trifluoromethyl)- H pyridin-3-yl 1.293 H H H H 2,6-bis(trifluoromethyl)- H pyridin-4-yl 1.294 H H H H 3,5-bis(trifluoromethyl)- H pyridin-2-yl 1.295 H H H H 2-thienyl H 1.296 H H H H 3-thienyl H 1.297 H H H H 5-cyanothien-2-yl H 1.298 H H H H 2-furyl H 1.299 H H H H 3-furyl H 1.300 H H H H 1-methyl-1,2,3-triazol-4-yl H 1.301 H H H H 2-methylthiopyrimidin-4-yl H 1.302 H H H H 5-methyl-2-methyl- H thiopyrimidin-4-yl 1.303 H H H H pyrazin-2-yl H 1.304 H H H H 3,6-dimethylpyrazin-2-yl H 1.305 H H H H 3-cyanopyrazin-2-yl H 1.306 H H H H quinolin-2-yl H 1.307 H H H H 3-ethylquinolin-2-yl H 1.308 H H H H benzyl H 1.309 H H H H 4-fluorobenzyl H 1.310 H H H H 4-chlorobenzyl H 1.311 H H H H 4-methylbenzyl H 1.312 H H H H 2,4-dimethylbenzyl H 1.313 H H H H 2,4,6-trimethylbenzyl H 1.314 H H H H CH₃ CH₃ 1.315 H H H H CH₂CH₃ CH₃ 1.316 H H H H n-propyl CH₃ 1.317 H H H H isopropyl CH₃ 1.318 H H H H n-butyl CH₃ 1.319 H H H H isobutyl CH₃ 1.320 H H H H sec-butyl CH₃ 1.321 H H H H tert-butyl CH₃ 1.322 H H H H vinyl CH₃ 1.323 H H H H ethynyl CH₃ 1.324 H H H H trimethylsilylethynyl CH₃ 1.325 H H H H CH₂OH CH₃ 1.326 H H H H CH₂OCH₃ CH₃ 1.327 H H H H CH₂OCH₂CH₃ CH₃ 1.328 H H H H CH₂OCH₂OCH₃ CH₃ 1.329 H H H H CH₂OCH₂OCH₂CH₃ CH₃ 1.330 H H H H CH₂OCH₂CH₂OCH₃ CH₃ 1.331 H H H H CHO CH₃ 1.332 H H H H COCH₃ CH₃ 1.333 H H H H CO₂H CH₃ 1.337 H H H H CO₂CH₃ CH₃ 1.335 H H H H CO₂CH₂CH₃ CH₃ 1.336 H H H H CONH₂ CH₃ 1.337 H H H H CONHCH₃ CH₃ 1.338 H H H H CONHCH₂CH₃ CH₃ 1.339 H H H H CON(CH₃)₂ CH₃ 1.340 H H H H CON(CH₂—CH₃)₂ CH₃ 1.341 H H H H CON(CH₃)OCH₃ CH₃ 1.342 H H H H CH═NOH CH₃ 1.343 H H H H CH═N—OCH₃ CH₃ 1.344 H H H H CH═N—OCH₂CH₃ CH₃ 1.345 H H H H C(CH₃)═N—OH CH₃ 1.346 H H H H C(CH₃)═N—OCH₃ CH₃ 1.347 H H H H CH₂OC(O)—NHCH₃ CH₃ 1.348 H H H H CH₂NH₂ CH₃ 1.349 H H H H CH₂NHCHO CH₃ 1.350 H H H H CH₂NHC(O)CH₃ CH₃ 1.351 H H H H CH₂NHC(O)OCH₃ CH₃ 1.352 H H H H NHCO₂CH₃ CH₃ 1.353 H H H H NHCO₂C(CH₃)₃ CH₃ 1.354 H H H H CH(OH)CH₃ CH₃ 1.355 H H H H CH(CH₃)OCH₃ CH₃ 1.356 H H H H CN CH₃ 1.357 H H H H CH₂SCH₃ CH₃ 1.358 H H H H CH₂S(O)CH₃ CH₃ 1.359 H H H H CH₂SO₂CH₃ CH₃ 1.360 H H H H CH₂SCH₂CH₃ CH₃ 1.361 H H H H CH₂S(O)CH₂CH₃ CH₃ 1.362 H H H H CH₂SO₂CH₂CH₃ CH₃ 1.363 H H H H OCH₃ CH₃ 1.364 H H H H OCH₂CH₃ CH₃ 1.365 H H H H CH(OCH₃)₂ CH₃ 1.366 H H H H CH(OCH₂CH₃)₂ CH₃ 1.367 H H H H cyclopropyl CH₃ 1.368 H H H H cyclobutyl CH₃ 1.369 H H H H cyclopentyl CH₃ 1.370 H H H H cyclohexyl CH₃ 1.371 H H H H F CH₃ 1.372 H H H H Cl CH₃ 1.373 H H H H Br CH₃ 1.374 H H H H I CH₃ 1.375 H H H H OH CH₃ 1.376 H H H H phenyl CH₃ 1.377 H H H H 2-acetylphenyl CH₃ 1.378 H H H H 3-acetylphenyl CH₃ 1.379 H H H H 4-acetylphenyl CH₃ 1.380 H H H H 2-chlorophenyl CH₃ 1.381 H H H H 3-chlorophenyl CH₃ 1.382 H H H H 4-chlorophenyl CH₃ 1.383 H H H H 2-cyanophenyl CH₃ 1.384 H H H H 3-cyanophenyl CH₃ 1.385 H H H H 4-cyanophenyl CH₃ 1.386 H H H H 2-fluorophenyl CH₃ 1.387 H H H H 3-fluorophenyl CH₃ 1.388 H H H H 4-fluorophenyl CH₃ 1.389 H H H H 2-methoxyphenyl CH₃ 1.390 H H H H 3-methoxyphenyl CH₃ 1.391 H H H H 4-methoxyphenyl CH₃ 1.392 H H H H 2-methylphenyl CH₃ 1.393 H H H H 3-methylphenyl CH₃ 1.394 H H H H 4-methylphenyl CH₃ 1.395 H H H H 2-nitrophenyl CH₃ 1.396 H H H H 3-nitrophenyl CH₃ 1.397 H H H H 4-nitrophenyl CH₃ 1.398 H H H H 2-thiomethylphenyl CH₃ 1.399 H H H H 3-thiomethylphenyl CH₃ 1.400 H H H H 4-thiomethylphenyl CH₃ 1.401 H H H H 2-trifluoromethoxyphenyl CH₃ 1.402 H H H H 3-trifluoromethoxyphenyl CH₃ 1.403 H H H H 4-trifluoromethoxyphenyl CH₃ 1.404 H H H H 2-trifluoromethylphenyl CH₃ 1.405 H H H H 3-trifluoromethylphenyl CH₃ 1.406 H H H H 4-trifluoromethylphenyl CH₃ 1.407 H H H H 2,3-dichlorophenyl CH₃ 1.408 H H H H 2,4-dichlorophenyl CH₃ 1.409 H H H H 2,5-dichlorophenyl CH₃ 1.410 H H H H 2,6-dichlorophenyl CH₃ 1.411 H H H H 3,4-dichlorophenyl CH₃ 1.412 H H H H 3,5-dichlorophenyl CH₃ 1.413 H H H H 2,3-difluorophenyl CH₃ 1.414 H H H H 2,4-difluorophenyl CH₃ 1.415 H H H H 2,5-difluorophenyl CH₃ 1.416 H H H H 2,6-difluorophenyl CH₃ 1.417 H H H H 3,4-difluorophenyl CH₃ 1.418 H H H H 3,5-difluorophenyl CH₃ 1.419 H H H H 2,4,6-trifluorophenyl CH₃ 1.420 H H H H 2,4-dimethylphenyl CH₃ 1.421 H H H H 2,4,6-trimethylphenyl CH₃ 1.422 H H H H 3,4,5-trimethoxyphenyl CH₃ 1.423 H H H H 2-chloro-3-cyanophenyl CH₃ 1.424 H H H H 2-chloro-4-cyanophenyl CH₃ 1.425 H H H H 2-chloro-5-cyanophenyl CH₃ 1.426 H H H H 2-chloro-6-cyanophenyl CH₃ 1.427 H H H H 3-chloro-2-cyanophenyl CH₃ 1.428 H H H H 3-chloro-4-cyanophenyl CH₃ 1.429 H H H H 3-chloro-5-cyanophenyl CH₃ 1.430 H H H H 5-chloro-2-cyanophenyl CH₃ 1.431 H H H H 4-chloro-2-cyanophenyl CH₃ 1.432 H H H H 4-chloro-3-cyanophenyl CH₃ 1.433 H H H H 2-chloro-3-fluorophenyl CH₃ 1.434 H H H H 2-chloro-4-fluorophenyl CH₃ 1.435 H H H H 2-chloro-5-fluorophenyl CH₃ 1.436 H H H H 2-chloro-6-fluorophenyl CH₃ 1.437 H H H H 3-chloro-2-fluorophenyl CH₃ 1.438 H H H H 3-chloro-4-fluorophenyl CH₃ 1.439 H H H H 3-chloro-5-fluorophenyl CH₃ 1.440 H H H H 5-chloro-2-fluorophenyl CH₃ 1.441 H H H H 4-chloro-2-fluorophenyl CH₃ 1.442 H H H H 4-chloro-3-fluorophenyl CH₃ 1.443 H H H H 2-chloro-3-methylphenyl CH₃ 1.444 H H H H 2-chloro-4-methylphenyl CH₃ 1.445 H H H H 2-chloro-5-methylphenyl CH₃ 1.446 H H H H 2-chloro-6-methylphenyl CH₃ 1.447 H H H H 3-chloro-2-methylphenyl CH₃ 1.448 H H H H 3-chloro-4-methylphenyl CH₃ 1.449 H H H H 3-chloro-5-methylphenyl CH₃ 1.450 H H H H 5-chloro-2-methylphenyl CH₃ 1.451 H H H H 4-chloro-2-methylphenyl CH₃ 1.452 H H H H 4-chloro-3-methylphenyl CH₃ 1.453 H H H H 2-cyano-3-fluorophenyl CH₃ 1.454 H H H H 2-cyano-4-fluorophenyl CH₃ 1.455 H H H H 2-cyano-5-fluorophenyl CH₃ 1.456 H H H H 2-cyano-6-fluorophenyl CH₃ 1.457 H H H H 3-cyano-2-fluorophenyl CH₃ 1.458 H H H H 3-cyano-4-fluorophenyl CH₃ 1.459 H H H H 3-cyano-5-fluorophenyl CH₃ 1.460 H H H H 5-cyano-2-fluorophenyl CH₃ 1.461 H H H H 4-cyano-2-fluorophenyl CH₃ 1.462 H H H H 4-cyano-3-fluorophenyl CH₃ 1.463 H H H H 2-fluoro-3-methylphenyl CH₃ 1.464 H H H H 2-fluoro-4-methylphenyl CH₃ 1.465 H H H H 2-fluoro-5-methylphenyl CH₃ 1.466 H H H H 2-fluoro-6-methylphenyl CH₃ 1.467 H H H H 3-fluoro-2-methylphenyl CH₃ 1.468 H H H H 3-fluoro-4-methylphenyl CH₃ 1.469 H H H H 3-fluoro-5-methylphenyl CH₃ 1.470 H H H H 5-fluoro-2-methylphenyl CH₃ 1.471 H H H H 4-fluoro-2-methylphenyl CH₃ 1.472 H H H H 4-fluoro-3-methylphenyl CH₃ 1.473 H H H H pyridin-2-yl CH₃ 1.474 H H H H pyridin-3-yl CH₃ 1.475 H H H H pyridin-4-yl CH₃ 1.476 H H H H 3-chloropyridin-2-yl CH₃ 1.477 H H H H 4-chloropyridin-2-yl CH₃ 1.478 H H H H 5-chloropyridin-2-yl CH₃ 1.479 H H H H 6-chloropyridin-2-yl CH₃ 1.480 H H H H 2-chloropyridin-3-yl CH₃ 1.481 H H H H 4-chloropyridin-3-yl CH₃ 1.482 H H H H 5-chloropyridin-3-yl CH₃ 1.483 H H H H 2-chloropyridin-4-yl CH₃ 1.484 H H H H 3-chloropyridin-4-yl CH₃ 1.485 H H H H 2-chloropyridin-5-yl CH₃ 1.486 H H H H 3-cyanopyridin-2-yl CH₃ 1.487 H H H H 4-cyanopyridin-2-yl CH₃ 1.488 H H H H 5-cyanopyridin-2-yl CH₃ 1.489 H H H H 6-cyanopyridin-2-yl CH₃ 1.490 H H H H 2-cyanopyridin-3-yl CH₃ 1.491 H H H H 4-cyanopyridin-3-yl CH₃ 1.492 H H H H 5-cyanopyridin-3-yl CH₃ 1.493 H H H H 2-cyanopyridin-5-yl CH₃ 1.494 H H H H 3-fluoropyridin-2-yl CH₃ 1.495 H H H H 4-fluoropyridin-2-yl CH₃ 1.496 H H H H 5-fluoropyridin-2-yl CH₃ 1.497 H H H H 6-fluoropyridin-2-yl CH₃ 1.498 H H H H 2-fluoropyridin-3-yl CH₃ 1.499 H H H H 4-fluoropyridin-3-yl CH₃ 1.500 H H H H 5-fluoropyridin-3-yl CH₃ 1.501 H H H H 2-fluoropyridin-5-yl CH₃ 1.502 H H H H 3-nitropyridin-2-yl CH₃ 1.503 H H H H 4-nitropyridin-2-yl CH₃ 1.504 H H H H 5-nitropyridin-2-yl CH₃ 1.505 H H H H 6-nitropyridin-2-yl CH₃ 1.506 H H H H 2-nitropyridin-3-yl CH₃ 1.507 H H H H 4-nitropyridin-3-yl CH₃ 1.508 H H H H 5-nitropyridin-3-yl CH₃ 1.509 H H H H 2-nitropyridin-5-yl CH₃ 1.510 H H H H 3-trifluoromethylpyridin-2-yl CH₃ 1.511 H H H H 4-trifluoromethylpyridin-2-yl CH₃ 1.512 H H H H 5-trifluoromethylpyridin-2-yl CH₃ 1.513 H H H H 6-trifluoromethylpyridin-2-yl CH₃ 1.514 H H H H 2-trifluoromethylpyridin-3-yl CH₃ 1.515 H H H H 4-trifluoromethylpyridin-3-yl CH₃ 1.516 H H H H 5-trifluoromethylpyridin-3-yl CH₃ 1.517 H H H H 2-trifluoromethylpyridin-5-yl CH₃ 1.518 H H H H 2,6-bis(trifluoromethyl) CH₃ pyridin-3-yl 1.519 H H H H 2,6-bis(trifluoromethyl) CH₃ pyridin-4-yl 1.520 H H H H 3,5-bis(trifluoromethyl)- CH₃ pyridin-2-yl 1.521 H H H H 2-thienyl CH₃ 1.522 H H H H 3-thienyl CH₃ 1.523 H H H H 5-cyanothien-2-yl CH₃ 1.524 H H H H 2-furyl CH₃ 1.525 H H H H 3-furyl CH₃ 1.526 H H H H 1-methyl-1,2,3-triazol-4-yl CH₃ 1.527 H H H H 2-methylthiopyrimidin-4-yl CH₃ 1.528 H H H H 5-methyl-2-methyl- CH₃ thiopyrimidin-4-yl 1.529 H H H H pyrazin-2-yl CH₃ 1.530 H H H H 3,6-dimethylpyrazin-2-yl CH₃ 1.531 H H H H 3-cyanopyrazin-2-yl CH₃ 1.532 H H H H quinolin-2-yl CH₃ 1.533 H H H H 3-ethylquinolin-2-yl CH₃ 1.534 H H H H benzyl CH₃ 1.535 H H H H 4-fluorobenzyl CH₃ 1.536 H H H H 4-chlorobenzyl CH₃ 1.537 H H H H 4-methylbenzyl CH₃ 1.538 H H H H 2,4-dimethylbenzyl CH₃ 1.539 H H H H 2,4,6-trimethylbenzyl CH₃ 1.540 CH₃ H H H CH₃ H 1.541 CH₃ H H H CH₂CH₃ H 1.542 CH₃ H H H n-propyl H 1.543 CH₃ H H H isopropyl H 1.544 CH₃ H H H n-butyl H 1.545 CH₃ H H H isobutyl H 1.546 CH₃ H H H sec-butyl H 1.547 CH₃ H H H tert-butyl H 1.548 CH₃ H H H vinyl H 1.549 CH₃ H H H ethynyl H 1.550 CH₃ H H H trimethylsilylethynyl H 1.551 CH₃ H H H CH₂OH H 1.552 CH₃ H H H CH₂OCH₃ H 1.553 CH₃ H H H CH₂OCH₂CH₃ H 1.554 CH₃ H H H CH₂OCH₂OCH₃ H 1.555 CH₃ H H H CH₂OCH₂OCH₂CH₃ H 1.556 CH₃ H H H CH₂OCH₂CH₂OCH₃ H 1.557 CH₃ H H H CHO H 1.558 CH₃ H H H COCH₃ H 1.559 CH₃ H H H CO₂H H 1.560 CH₃ H H H CO₂CH₃ H 1.561 CH₃ H H H CO₂CH₂CH₃ H 1.562 CH₃ H H H CONH₂ H 1.563 CH₃ H H H CONHCH₃ H 1.564 CH₃ H H H CONHCH₂CH₃ H 1.565 CH₃ H H H CON(CH₃)₂ H 1.566 CH₃ H H H CON(CH₂—CH₃)₂ H 1.567 CH₃ H H H CON(CH₃)OCH₃ H 1.568 CH₃ H H H CH═NOH H 1.569 CH₃ H H H CH═N—OCH₃ H 1.570 CH₃ H H H CH═N—OCH₂CH₃ H 1.571 CH₃ H H H C(CH₃)═N—OH H 1.572 CH₃ H H H C(CH₃)═N—OCH₃ H 1.573 CH₃ H H H CH₂OC(O)—NHCH₃ H 1.574 CH₃ H H H CH₂NH₂ H 1.575 CH₃ H H H CH₂NHCHO H 1.576 CH₃ H H H CH₂NHC(O)CH₃ H 1.577 CH₃ H H H CH₂NHC(O)OCH₃ H 1.578 CH₃ H H H NHCO₂CH₃ H 1.579 CH₃ H H H NHCO₂C(CH₃)₃ H 1.580 CH₃ H H H CH(OH)CH₃ H 1.581 CH₃ H H H CH(CH₃)OCH₃ H 1.582 CH₃ H H H CN H 1.583 CH₃ H H H CH₂SCH₃ H 1.584 CH₃ H H H CH₂S(O)CH₃ H 1.585 CH₃ H H H CH₂SO₂CH₃ H 1.586 CH₃ H H H CH₂SCH₂CH₃ H 1.587 CH₃ H H H CH₂S(O)CH₂CH₃ H 1.588 CH₃ H H H CH₂SO₂CH₂CH₃ H 1.589 CH₃ H H H OCH₃ H 1.590 CH₃ H H H OCH₂CH₃ H 1.591 CH₃ H H H CH(OCH₃)₂ H 1.592 CH₃ H H H CH(OCH₂CH₃)₂ H 1.593 CH₃ H H H cyclopropyl H 1.594 CH₃ H H H cyclobutyl H 1.595 CH₃ H H H cyclopentyl H 1.596 CH₃ H H H cyclohexyl H 1.597 CH₃ H H H F H 1.598 CH₃ H H H Cl H 1.599 CH₃ H H H Br H 1.600 CH₃ H H H I H 1.601 CH₃ H H H OH H 1.602 CH₃ H H H phenyl H 1.603 CH₃ H H H 2-acetylphenyl H 1.604 CH₃ H H H 3-acetylphenyl H 1.605 CH₃ H H H 4-acetylphenyl H 1.606 CH₃ H H H 2-chlorophenyl H 1.607 CH₃ H H H 3-chlorophenyl H 1.608 CH₃ H H H 4-chlorophenyl H 1.609 CH₃ H H H 2-cyanophenyl H 1.610 CH₃ H H H 3-cyanophenyl H 1.611 CH₃ H H H 4-cyanophenyl H 1.612 CH₃ H H H 2-fluorophenyl H 1.613 CH₃ H H H 3-fluorophenyl H 1.614 CH₃ H H H 4-fluorophenyl H 1.615 CH₃ H H H 2-methoxyphenyl H 1.616 CH₃ H H H 3-methoxyphenyl H 1.617 CH₃ H H H 4-methoxyphenyl H 1.618 CH₃ H H H 2-methylphenyl H 1.619 CH₃ H H H 3-methylphenyl H 1.620 CH₃ H H H 4-methylphenyl H 1.621 CH₃ H H H 2-nitrophenyl H 1.622 CH₃ H H H 3-nitrophenyl H 1.623 CH₃ H H H 4-nitrophenyl H 1.624 CH₃ H H H 2-thiomethylphenyl H 1.625 CH₃ H H H 3-thiomethylphenyl H 1.626 CH₃ H H H 4-thiomethylphenyl H 1.627 CH₃ H H H 2-trifluoromethoxyphenyl H 1.628 CH₃ H H H 3-trifluoromethoxyphenyl H 1.629 CH₃ H H H 4-trifluoromethoxyphenyl H 1.630 CH₃ H H H 2-trifluoromethylphenyl H 1.631 CH₃ H H H 3-trifluoromethylphenyl H 1.632 CH₃ H H H 4-trifluoromethylphenyl H 1.633 CH₃ H H H 2,3-dichlorophenyl H 1.634 CH₃ H H H 2,4-dichlorophenyl H 1.635 CH₃ H H H 2,5-dichlorophenyl H 1.636 CH₃ H H H 2,6-dichlorophenyl H 1.637 CH₃ H H H 3,4-dichlorophenyl H 1.638 CH₃ H H H 3,5-dichlorophenyl H 1.639 CH₃ H H H 2,3-difluorophenyl H 1.640 CH₃ H H H 2,4-difluorophenyl H 1.641 CH₃ H H H 2,5-difluorophenyl H 1.642 CH₃ H H H 2,6-difluorophenyl H 1.643 CH₃ H H H 3,4-difluorophenyl H 1.644 CH₃ H H H 3,5-difluorophenyl H 1.645 CH₃ H H H 2,4,6-trifluorophenyl H 1.646 CH₃ H H H 2,4-dimethylphenyl H 1.647 CH₃ H H H 2,4,6-trimethylphenyl H 1.648 CH₃ H H H 3,4,5-trimethoxy-phenyl H 1.649 CH₃ H H H 2-chloro-3-cyanophenyl H 1.650 CH₃ H H H 2-chloro-4-cyanophenyl H 1.651 CH₃ H H H 2-chloro-5-cyanophenyl H 1.652 CH₃ H H H 2-chloro-6-cyanophenyl H 1.653 CH₃ H H H 3-chloro-2-cyanophenyl H 1.654 CH₃ H H H 3-chloro-4-cyanophenyl H 1.655 CH₃ H H H 3-chloro-5-cyanophenyl H 1.656 CH₃ H H H 5-chloro-2-cyanophenyl H 1.657 CH₃ H H H 4-chloro-2-cyanophenyl H 1.658 CH₃ H H H 4-chloro-3-cyanophenyl H 1.659 CH₃ H H H 2-chloro-3-fluorophenyl H 1.660 CH₃ H H H 2-chloro-4-fluorophenyl H 1.661 CH₃ H H H 2-chloro-5-fluorophenyl H 1.662 CH₃ H H H 2-chloro-6-fluorophenyl H 1.663 CH₃ H H H 3-chloro-2-fluorophenyl H 1.664 CH₃ H H H 3-chloro-4-fluorophenyl H 1.665 CH₃ H H H 3-chloro-5-fluorophenyl H 1.666 CH₃ H H H 5-chloro-2-fluorophenyl H 1.667 CH₃ H H H 4-chloro-2-fluorophenyl H 1.668 CH₃ H H H 4-chloro-3-fluorophenyl H 1.669 CH₃ H H H 2-chloro-3-methylphenyl H 1.670 CH₃ H H H 2-chloro-4-methylphenyl H 1.671 CH₃ H H H 2-chloro-5-methylphenyl H 1.672 CH₃ H H H 2-chloro-6-methylphenyl H 1.673 CH₃ H H H 3-chloro-2-methylphenyl H 1.674 CH₃ H H H 3-chloro-4-methylphenyl H 1.675 CH₃ H H H 3-chloro-5-methylphenyl H 1.676 CH₃ H H H 5-chloro-2-methylphenyl H 1.677 CH₃ H H H 4-chloro-2-methylphenyl H 1.678 CH₃ H H H 4-chloro-3-methylphenyl H 1.679 CH₃ H H H 2-cyano-3-fluorophenyl H 1.680 CH₃ H H H 2-cyano-4-fluorophenyl H 1.681 CH₃ H H H 2-cyano-5-fluorophenyl H 1.682 CH₃ H H H 2-cyano-6-fluorophenyl H 1.683 CH₃ H H H 3-cyano-2-fluorophenyl H 1.684 CH₃ H H H 3-cyano-4-fluorophenyl H 1.685 CH₃ H H H 3-cyano-5-fluorophenyl H 1.686 CH₃ H H H 5-cyano-2-fluorophenyl H 1.687 CH₃ H H H 4-cyano-2-fluorophenyl H 1.688 CH₃ H H H 4-cyano-3-fluorophenyl H 1.689 CH₃ H H H 2-fluoro-3-methylphenyl H 1.690 CH₃ H H H 2-fluoro-4-methylphenyl H 1.691 CH₃ H H H 2-fluoro-5-methylphenyl H 1.692 CH₃ H H H 2-fluoro-6-methylphenyl H 1.693 CH₃ H H H 3-fluoro-2-methylphenyl H 1.694 CH₃ H H H 3-fluoro-4-methylphenyl H 1.695 CH₃ H H H 3-fluoro-5-methylphenyl H 1.696 CH₃ H H H 5-fluoro-2-methylphenyl H 1.697 CH₃ H H H 4-fluoro-2-methylphenyl H 1.698 CH₃ H H H 4-fluoro-3-methylphenyl H 1.699 CH₃ H H H pyridin-2-yl H 1.700 CH₃ H H H pyridin-3-yl H 1.701 CH₃ H H H pyridin-4-yl H 1.702 CH₃ H H H 3-chloropyridin-2-yl H 1.703 CH₃ H H H 4-chloropyridin-2-yl H 1.704 CH₃ H H H 5-chloropyridin-2-yl H 1.705 CH₃ H H H 6-chloropyridin-2-yl H 1.706 CH₃ H H H 2-chloropyridin-3-yl H 1.707 CH₃ H H H 4-chloropyridin-3-yl H 1.708 CH₃ H H H 5-chloropyridin-3-yl H 1.709 CH₃ H H H 2-chloropyridin-4-yl H 1.710 CH₃ H H H 3-chloropyridin-4-yl H 1.711 CH₃ H H H 2-chloropyridin-5-yl H 1.712 CH₃ H H H 3-cyanopyridin-2-yl H 1.713 CH₃ H H H 4-cyanopyridin-2-yl H 1.714 CH₃ H H H 5-cyanopyridin-2-yl H 1.715 CH₃ H H H 6-cyanopyridin-2-yl H 1.716 CH₃ H H H 2-cyanopyridin-3-yl H 1.717 CH₃ H H H 4-cyanopyridin-3-yl H 1.718 CH₃ H H H 5-cyanopyridin-3-yl H 1.719 CH₃ H H H 2-cyanopyridin-5-yl H 1.720 CH₃ H H H 3-fluoropyridin-2-yl H 1.721 CH₃ H H H 4-fluoropyridin-2-yl H 1.722 CH₃ H H H 5-fluoropyridin-2-yl H 1.723 CH₃ H H H 6-fluoropyridin-2-yl H 1.724 CH₃ H H H 2-fluoropyridin-3-yl H 1.725 CH₃ H H H 4-fluoropyridin-3-yl H 1.726 CH₃ H H H 5-fluoropyridin-3-yl H 1.727 CH₃ H H H 2-fluoropyridin-5-yl H 1.728 CH₃ H H H 3-nitropyridin-2-yl H 1.729 CH₃ H H H 4-nitropyridin-2-yl H 1.730 CH₃ H H H 5-nitropyridin-2-yl H 1.731 CH₃ H H H 6-nitropyridin-2-yl H 1.732 CH₃ H H H 2-nitropyridin-3-yl H 1.733 CH₃ H H H 4-nitropyridin-3-yl H 1.734 CH₃ H H H 5-nitropyridin-3-yl H 1.735 CH₃ H H H 2-nitropyridin-5-yl H 1.736 CH₃ H H H 3-trifluoromethylpyridin-2-yl H 1.737 CH₃ H H H 4-trifluoromethylpyridin-2-yl H 1.738 CH₃ H H H 5-trifluoromethylpyridin-2-yl H 1.739 CH₃ H H H 6-trifluoromethylpyridin-2-yl H 1.740 CH₃ H H H 2-trifluoromethylpyridin-3-yl H 1.741 CH₃ H H H 4-trifluoromethylpyridin-3-yl H 1.742 CH₃ H H H 5-trifluoromethylpyridin-3-yl H 1.743 CH₃ H H H 2-trifluoromethylpyridin-5-yl H 1.744 CH₃ H H H 2,6-bis(trifluoromethyl)- H pyridin-3-yl 1.745 CH₃ H H H 2,6-bis(trifluoromethyl)- H pyridin-4-yl 1.746 CH₃ H H H 3,5-bis(trifluoromethyl)- H pyridin-2-yl 1.747 CH₃ H H H 2-thienyl H 1.748 CH₃ H H H 3-thienyl H 1.749 CH₃ H H H 5-cyanothien-2-yl H 1.750 CH₃ H H H 2-furyl H 1.751 CH₃ H H H 3-furyl H 1.752 CH₃ H H H 1-methyl-1,2,3-triazol-4-yl H 1.753 CH₃ H H H 2-methylthiopyrimidin-4-yl H 1.754 CH₃ H H H 5-methyl-2-methyl- H thiopyrimidin-4-yl 1.755 CH₃ H H H pyrazin-2-yl H 1.756 CH₃ H H H 3,6-dimethylpyrazin-2-yl H 1.757 CH₃ H H H 3-cyanopyrazin-2-yl H 1.758 CH₃ H H H quinolin-2-yl H 1.759 CH₃ H H H 3-ethylquinolin-2-yl H 1.760 CH₃ H H H benzyl H 1.761 CH₃ H H H 4-fluorobenzyl H 1.762 CH₃ H H H 4-chlorobenzyl H 1.763 CH₃ H H H 4-methylbenzyl H 1.764 CH₃ H H H 2,4-dimethylbenzyl H 1.765 CH₃ H H H 2,4,6-trimethylbenzyl H 1.766 CH₃ H H H H CH₃ 1.767 CH₃ H H H CH₃ CH₃ 1.768 CH₃ H H H CH₂CH₃ CH₃ 1.769 CH₃ H H H n-propyl CH₃ 1.770 CH₃ H H H isopropyl CH₃ 1.771 CH₃ H H H n-butyl CH₃ 1.772 CH₃ H H H isobutyl CH₃ 1.773 CH₃ H H H sec-butyl CH₃ 1.774 CH₃ H H H tert-butyl CH₃ 1.775 CH₃ H H H vinyl CH₃ 1.776 CH₃ H H H ethynyl CH₃ 1.777 CH₃ H H H trimethylsilylethynyl CH₃ 1.778 CH₃ H H H CH₂OH CH₃ 1.779 CH₃ H H H CH₂OCH₃ CH₃ 1.780 CH₃ H H H CH₂OCH₂CH₃ CH₃ 1.781 CH₃ H H H CH₂OCH₂OCH₃ CH₃ 1.782 CH₃ H H H CH₂OCH₂OCH₂CH₃ CH₃ 1.783 CH₃ H H H CH₂OCH₂CH₂OCH₃ CH₃ 1.784 CH₃ H H H CHO CH₃ 1.785 CH₃ H H H COCH₃ CH₃ 1.786 CH₃ H H H CO₂H CH₃ 1.787 CH₃ H H H CO₂CH₃ CH₃ 1.788 CH₃ H H H CO₂CH₂CH₃ CH₃ 1.789 CH₃ H H H CONH₂ CH₃ 1.790 CH₃ H H H CONHCH₃ CH₃ 1.791 CH₃ H H H CONHCH₂CH₃ CH₃ 1.792 CH₃ H H H CON(CH₃)₂ CH₃ 1.793 CH₃ H H H CON(CH₂—CH₃)₂ CH₃ 1.794 CH₃ H H H CON(CH₃)OCH₃ CH₃ 1.795 CH₃ H H H CH═NOH CH₃ 1.796 CH₃ H H H CH═N—OCH₃ CH₃ 1.797 CH₃ H H H CH═N—OCH₂CH₃ CH₃ 1.798 CH₃ H H H C(CH₃)═N—OH CH₃ 1.799 CH₃ H H H C(CH₃)═N—OCH₃ CH₃ 1.800 CH₃ H H H CH₂OC(O)—NHCH₃ CH₃ 1.801 CH₃ H H H CH₂NH₂ CH₃ 1.802 CH₃ H H H CH₂NHCHO CH₃ 1.803 CH₃ H H H CH₂NHC(O)CH₃ CH₃ 1.804 CH₃ H H H CH₂NHC(O)OCH₃ CH₃ 1.805 CH₃ H H H NHCO₂CH₃ CH₃ 1.806 CH₃ H H H NHCO₂C(CH₃)₃ CH₃ 1.807 CH₃ H H H CH(OH)CH₃ CH₃ 1.808 CH₃ H H H CH(CH₃)OCH₃ CH₃ 1.809 CH₃ H H H CN CH₃ 1.810 CH₃ H H H CH₂SCH₃ CH₃ 1.811 CH₃ H H H CH₂S(O)CH₃ CH₃ 1.812 CH₃ H H H CH₂SO₂CH₃ CH₃ 1.813 CH₃ H H H CH₂SCH₂CH₃ CH₃ 1.814 CH₃ H H H CH₂S(O)CH₂CH₃ CH₃ 1.815 CH₃ H H H CH₂SO₂CH₂CH₃ CH₃ 1.816 CH₃ H H H OCH₃ CH₃ 1.817 CH₃ H H H OCH₂CH₃ CH₃ 1.818 CH₃ H H H CH(OCH₃)₂ CH₃ 1.819 CH₃ H H H CH(OCH₂CH₃)₂ CH₃ 1.820 CH₃ H H H Cyclopropyl CH₃ 1.821 CH₃ H H H Cyclobutyl CH₃ 1.822 CH₃ H H H Cyclopentyl CH₃ 1.823 CH₃ H H H Cyclohexyl CH₃ 1.824 CH₃ H H H F CH₃ 1.825 CH₃ H H H Cl CH₃ 1.826 CH₃ H H H Br CH₃ 1.827 CH₃ H H H I CH₃ 1.828 CH₃ H H H OH CH₃ 1.829 CH₃ H H H phenyl CH₃ 1.830 CH₃ H H H 2-acetylphenyl CH₃ 1.831 CH₃ H H H 3-acetylphenyl CH₃ 1.832 CH₃ H H H 4-acetylphenyl CH₃ 1.833 CH₃ H H H 2-chlorophenyl CH₃ 1.834 CH₃ H H H 3-chlorophenyl CH₃ 1.835 CH₃ H H H 4-chlorophenyl CH₃ 1.836 CH₃ H H H 2-cyanophenyl CH₃ 1.837 CH₃ H H H 3-cyanophenyl CH₃ 1.838 CH₃ H H H 4-cyanophenyl CH₃ 1.839 CH₃ H H H 2-fluorophenyl CH₃ 1.840 CH₃ H H H 3-fluorophenyl CH₃ 1.841 CH₃ H H H 4-fluorophenyl CH₃ 1.842 CH₃ H H H 2-methoxyphenyl CH₃ 1.843 CH₃ H H H 3-methoxyphenyl CH₃ 1.844 CH₃ H H H 4-methoxyphenyl CH₃ 1.845 CH₃ H H H 2-methylphenyl CH₃ 1.846 CH₃ H H H 3-methylphenyl CH₃ 1.847 CH₃ H H H 4-methylphenyl CH₃ 1.848 CH₃ H H H 2-nitrophenyl CH₃ 1.849 CH₃ H H H 3-nitrophenyl CH₃ 1.850 CH₃ H H H 4-nitrophenyl CH₃ 1.851 CH₃ H H H 2-thiomethylphenyl CH₃ 1.852 CH₃ H H H 3-thiomethylphenyl CH₃ 1.853 CH₃ H H H 4-thiomethylphenyl CH₃ 1.854 CH₃ H H H 2-trifluoromethoxyphenyl CH₃ 1.855 CH₃ H H H 3-trifluoromethoxyphenyl CH₃ 1.856 CH₃ H H H 4-trifluoromethoxyphenyl CH₃ 1.857 CH₃ H H H 2-trifluoromethylphenyl CH₃ 1.858 CH₃ H H H 3-trifluoromethylphenyl CH₃ 1.859 CH₃ H H H 4-trifluoromethylphenyl CH₃ 1.860 CH₃ H H H 2,3-dichlorophenyl CH₃ 1.861 CH₃ H H H 2,4-dichlorophenyl CH₃ 1.862 CH₃ H H H 2,5-dichlorophenyl CH₃ 1.863 CH₃ H H H 2,6-dichlorophenyl CH₃ 1.864 CH₃ H H H 3,4-dichlorophenyl CH₃ 1.865 CH₃ H H H 3,5-dichlorophenyl CH₃ 1.866 CH₃ H H H 2,3-difluorophenyl CH₃ 1.867 CH₃ H H H 2,4-difluorophenyl CH₃ 1.868 CH₃ H H H 2,5-difluorophenyl CH₃ 1.869 CH₃ H H H 2,6-difluorophenyl CH₃ 1.870 CH₃ H H H 3,4-difluorophenyl CH₃ 1.871 CH₃ H H H 3,5-difluorophenyl CH₃ 1.872 CH₃ H H H 2,4,6-trifluorophenyl CH₃ 1.873 CH₃ H H H 2,4-dimethylphenyl CH₃ 1.874 CH₃ H H H 2,4,6-trimethylphenyl CH₃ 1.875 CH₃ H H H 3,4,5-trimethoxyphenyl CH₃ 1.876 CH₃ H H H 2-chloro-3-cyanophenyl CH₃ 1.877 CH₃ H H H 2-chloro-4-cyanophenyl CH₃ 1.878 CH₃ H H H 2-chloro-5-cyanophenyl CH₃ 1.879 CH₃ H H H 2-chloro-6-cyanophenyl CH₃ 1.880 CH₃ H H H 3-chloro-2-cyanophenyl CH₃ 1.881 CH₃ H H H 3-chloro-4-cyanophenyl CH₃ 1.882 CH₃ H H H 3-chloro-5-cyanophenyl CH₃ 1.883 CH₃ H H H 5-chloro-2-cyanophenyl CH₃ 1.884 CH₃ H H H 4-chloro-2-cyanophenyl CH₃ 1.885 CH₃ H H H 4-chloro-3-cyanophenyl CH₃ 1.886 CH₃ H H H 2-chloro-3-fluorophenyl CH₃ 1.887 CH₃ H H H 2-chloro-4-fluorophenyl CH₃ 1.888 CH₃ H H H 2-chloro-5-fluorophenyl CH₃ 1.889 CH₃ H H H 2-chloro-6-fluorophenyl CH₃ 1.890 CH₃ H H H 3-chloro-2-fluorophenyl CH₃ 1.891 CH₃ H H H 3-chloro-4-fluorophenyl CH₃ 1.892 CH₃ H H H 3-chloro-5-fluorophenyl CH₃ 1.893 CH₃ H H H 5-chloro-2-fluorophenyl CH₃ 1.894 CH₃ H H H 4-chloro-2-fluorophenyl CH₃ 1.895 CH₃ H H H 4-chloro-3-fluorophenyl CH₃ 1.896 CH₃ H H H 2-chloro-3-methylphenyl CH₃ 1.897 CH₃ H H H 2-chloro-4-methylphenyl CH₃ 1.898 CH₃ H H H 2-chloro-5-methylphenyl CH₃ 1.899 CH₃ H H H 2-chloro-6-methylphenyl CH₃ 1.900 CH₃ H H H 3-chloro-2-methylphenyl CH₃ 1.901 CH₃ H H H 3-chloro-4-methylphenyl CH₃ 1.902 CH₃ H H H 3-chloro-5-methylphenyl CH₃ 1.903 CH₃ H H H 5-chloro-2-methylphenyl CH₃ 1.904 CH₃ H H H 4-chloro-2-methylphenyl CH₃ 1.905 CH₃ H H H 4-chloro-3-methylphenyl CH₃ 1.906 CH₃ H H H 2-cyano-3-fluorophenyl CH₃ 1.907 CH₃ H H H 2-cyano-4-fluorophenyl CH₃ 1.908 CH₃ H H H 2-cyano-5-fluorophenyl CH₃ 1.909 CH₃ H H H 2-cyano-6-fluorophenyl CH₃ 1.910 CH₃ H H H 3-cyano-2-fluorophenyl CH₃ 1.911 CH₃ H H H 3-cyano-4-fluorophenyl CH₃ 1.912 CH₃ H H H 3-cyano-5-fluorophenyl CH₃ 1.913 CH₃ H H H 5-cyano-2-fluorophenyl CH₃ 1.914 CH₃ H H H 4-cyano-2-fluorophenyl CH₃ 1.915 CH₃ H H H 4-cyano-3-fluorophenyl CH₃ 1.916 CH₃ H H H 2-fluoro-3-methylphenyl CH₃ 1.917 CH₃ H H H 2-fluoro-4-methylphenyl CH₃ 1.918 CH₃ H H H 2-fluoro-5-methylphenyl CH₃ 1.919 CH₃ H H H 2-fluoro-6-methylphenyl CH₃ 1.920 CH₃ H H H 3-fluoro-2-methylphenyl CH₃ 1.921 CH₃ H H H 3-fluoro-4-methylphenyl CH₃ 1.922 CH₃ H H H 3-fluoro-5-methylphenyl CH₃ 1.923 CH₃ H H H 5-fluoro-2-methylphenyl CH₃ 1.924 CH₃ H H H 4-fluoro-2-methylphenyl CH₃ 1.925 CH₃ H H H 4-fluoro-3-methylphenyl CH₃ 1.926 CH₃ H H H pyridin-2-yl CH₃ 1.927 CH₃ H H H pyridin-3-yl CH₃ 1.928 CH₃ H H H pyridin-4-yl CH₃ 1.929 CH₃ H H H 3-chloropyridin-2-yl CH₃ 1.930 CH₃ H H H 4-chloropyridin-2-yl CH₃ 1.931 CH₃ H H H 5-chloropyridin-2-yl CH₃ 1.932 CH₃ H H H 6-chloropyridin-2-yl CH₃ 1.933 CH₃ H H H 2-chloropyridin-3-yl CH₃ 1.934 CH₃ H H H 4-chloropyridin-3-yl CH₃ 1.935 CH₃ H H H 5-chloropyridin-3-yl CH₃ 1.936 CH₃ H H H 2-chloropyridin-4-yl CH₃ 1.937 CH₃ H H H 3-chloropyridin-4-yl CH₃ 1.938 CH₃ H H H 2-chloropyridin-5-yl CH₃ 1.939 CH₃ H H H 3-cyanopyridin-2-yl CH₃ 1.940 CH₃ H H H 4-cyanopyridin-2-yl CH₃ 1.941 CH₃ H H H 5-cyanopyridin-2-yl CH₃ 1.942 CH₃ H H H 6-cyanopyridin-2-yl CH₃ 1.943 CH₃ H H H 2-cyanopyridin-3-yl CH₃ 1.944 CH₃ H H H 4-cyanopyridin-3-yl CH₃ 1.945 CH₃ H H H 5-cyanopyridin-3-yl CH₃ 1.946 CH₃ H H H 2-cyanopyridin-5-yl CH₃ 1.947 CH₃ H H H 3-fluoropyridin-2-yl CH₃ 1.948 CH₃ H H H 4-fluoropyridin-2-yl CH₃ 1.949 CH₃ H H H 5-fluoropyridin-2-yl CH₃ 1.950 CH₃ H H H 6-fluoropyridin-2-yl CH₃ 1.951 CH₃ H H H 2-fluoropyridin-3-yl CH₃ 1.952 CH₃ H H H 4-fluoropyridin-3-yl CH₃ 1.953 CH₃ H H H 5-fluoropyridin-3-yl CH₃ 1.954 CH₃ H H H 2-fluoropyridin-5-yl CH₃ 1.955 CH₃ H H H 3-nitropyridin-2-yl CH₃ 1.956 CH₃ H H H 4-nitropyridin-2-yl CH₃ 1.957 CH₃ H H H 5-nitropyridin-2-yl CH₃ 1.958 CH₃ H H H 6-nitropyridin-2-yl CH₃ 1.959 CH₃ H H H 2-nitropyridin-3-yl CH₃ 1.960 CH₃ H H H 4-nitropyridin-3-yl CH₃ 1.961 CH₃ H H H 5-nitropyridin-3-yl CH₃ 1.962 CH₃ H H H 2-nitropyridin-5-yl CH₃ 1.963 CH₃ H H H 3-trifluoromethylpyridin-2-yl CH₃ 1.964 CH₃ H H H 4-trifluoromethylpyridin-2-yl CH₃ 1.965 CH₃ H H H 5-trifluoromethylpyridin-2-yl CH₃ 1.966 CH₃ H H H 6-trifluoromethylpyridin-2-yl CH₃ 1.967 CH₃ H H H 2-trifluoromethylpyridin-3-yl CH₃ 1.968 CH₃ H H H 4-trifluoromethylpyridin-3-yl CH₃ 1.969 CH₃ H H H 5-trifluoromethylpyridin-3-yl CH₃ 1.970 CH₃ H H H 2-trifluoromethylpyridin-5-yl CH₃ 1.971 CH₃ H H H 2,6-bis(trifluoromethyl)- CH₃ pyridin-3-yl 1.972 CH₃ H H H 2,6-bis(trifluoromethyl)- CH₃ pyridin-4-yl 1.973 CH₃ H H H 3,5-bis(trifluoromethyl)- CH₃ pyridin-2-yl 1.974 CH₃ H H H 2-thienyl CH₃ 1.975 CH₃ H H H 3-thienyl CH₃ 1.976 CH₃ H H H 5-cyanothien-2-yl CH₃ 1.977 CH₃ H H H 2-furyl CH₃ 1.978 CH₃ H H H 3-furyl CH₃ 1.979 CH₃ H H H 1-methyl-1,2,3-triazol-4-yl CH₃ 1.980 CH₃ H H H 2-methylthiopyrimidin-4-yl CH₃ 1.981 CH₃ H H H 5-methyl-2-methyl- CH₃ thiopyrimidin-4-yl 1.982 CH₃ H H H pyrazin-2-yl CH₃ 1.983 CH₃ H H H 3,6-dimethylpyrazin-2-yl CH₃ 1.984 CH₃ H H H 3-cyanopyrazin-2-yl CH₃ 1.985 CH₃ H H H quinolin-2-yl CH₃ 1.986 CH₃ H H H 3-ethylquinolin-2-yl CH₃ 1.987 CH₃ H H H benzyl CH₃ 1.988 CH₃ H H H 4-fluorobenzyl CH₃ 1.989 CH₃ H H H 4-chlorobenzyl CH₃ 1.990 CH₃ H H H 4-methylbenzyl CH₃ 1.991 CH₃ H H H 2,4-dimethylbenzyl CH₃ 1.992 CH₃ H H H 2,4,6-trimethylbenzyl CH₃ 1.993 CH₃ H H H H CH₂OH 1.994 CH₃ H H H H CH₂OCH₃ 1.995 CH₃ H H H H CH₂OCH₂CH₃ 1.996 CH₃ H H H H CHO 1.997 CH₃ H H H H COCH₃ 1.998 CH₃ H H H H CO₂H 1.999 CH₃ H H H H CO₂CH₃ 1.1000 CH₃ H H H H CO₂CH₂CH₃ 1.1001 CH₃ H H H H CONH₂ 1.1002 CH₃ H H H H CONHCH₃ 1.1003 CH₃ H H H H CONHCH₂CH₃ 1.1004 CH₃ H H H H CON(CH₃)₂ 1.1005 CH₃ H H H H CON—(CH₂CH₃)₂ 1.1006 CH₃ H H H H CON(CH₃)O—CH₃ 1.1007 CH₃ H H H H CH═NOH 1.1008 CH₃ H H H H CH═NOCH₃ 1.1009 CH₃ H H H H CH═NOCH₂—CH₃ 1.1010 CH₃ H H H H C(CH₃)═NOH 1.1011 CH₃ H H H H C(CH₃)═NO—CH₃ 1.1012 CH₃ H H H H CH₂OC(O)NH—CH₃ 1.1013 CH₃ H H H H CH₂NH₂ 1.1014 CH₃ H H H H CH₂NHCHO 1.1015 CH₃ H H H H CH₂NHC(O)—CH₃ 1.1016 CH₃ H H H H CH₂NHC(O)OCH₃ 1.1017 CH₃ H H H H NHCO₂CH₃ 1.1018 CH₃ H H H H NHCO₂—C(CH₃)₃ 1.1019 CH₃ H H H H CH(OH)CH₃ 1.1020 CH₃ H H H H CH(CH₃)OCH₃ 1.1021 CH₃ H H H H CN 1.1022 CH₃ H H H H CH₂SCH₃ 1.1023 CH₃ H H H H CH₂S(O)CH₃ 1.1024 CH₃ H H H H CH₂SO₂CH₃ 1.1025 CH₃ H H H H CH₂SCH₂CH₃ 1.1026 CH₃ H H H H CH₂S(O)CH₂—CH₃ 1.1027 CH₃ H H H H CH₂SO₂CH₂—CH₃ 1.1028 CH₃ H H H H OCH₃ 1.1029 CH₃ H H H H OCH₂CH₃ 1.1030 CH₃ H H H H CH(OCH₃)₂ 1.1031 CH₃ H H H H CH—(OCH₂CH₃)₂ 1.1032 CH₃ H H H H CH₂CH₃ 1.1033 CH₃ H H H H CH₂CH₂CH₃ 1.1034 CH₃ H H H H CH(CH₃)₂ 1.1035 CH₃ H H H H C(CH₃)₃ 1.1036 CH₃ H H H H CH₂CH(CH₃)₂ 1.1037 CH₃ H H H H CH₂C(CH₃)₃ 1.1038 CH₃ H H H H CH₂CN 1.1039 CH₃ H H H H cyclopropyl 1.1040 CH₃ H H H H cyclobutyl 1.1041 CH₃ H H H H cyclopentyl 1.1042 CH₃ H H H H cyclohexyl 1.1043 CH₃ H H H H CH₂-cyclopropyl 1.1044 CH₃ H H H H benzyl 1.1045 CH₃ H H H H CH₂CF₃ 1.1046 CH₃ CH₃ H H CH₃ CH₃ 1.1047 H H Cl Cl H H 1.1048 H H Cl Cl H CH₃ 1.1049 CH₃ H Cl Cl H CH₃ 1.1050 H H Br Br H H 1.1051 H H Br Br H CH₃ 1.1052 CH₃ H Br Br H CH₃ 1.1053 H H OH OH H H 1.1054 H H OH OH H CH₃ 1.1055 CH₃ H OH OH H CH₃ 1.1056 H H —O—C(CH₃)₂—O— H H 1.1057 H H —O—C(CH₃)₂—O— H CH₃ 1.1058 CH₃ H —O—C(CH₃)₂—O— H CH₃ 1.1059 H R⁷ and R⁸ form unit ═O H H H 1.1060 H R⁷ and R⁸ form unit ═O H H CH₃ 1.1061 CH₃ R⁷ and R⁸ form unit ═O H H H 1.1062 CH₃ R⁷ and R⁸ form unit ═O H H CH₃ 1.1063 H R⁷ and R⁸ form unit ═NOCH₃ H H H 1.1064 H R⁷ and R⁸ form unit ═NOCH₃ H H CH₃ 1.1065 CH₃ R⁷ and R⁸ form unit ═NOCH₃ H H H 1.1066 CH₃ R⁷ and R⁸ form unit ═NOCH₃ H H CH₃ 1.1067 H R⁷ and R⁸ form unit ═NOCH₂CH₃ H H H 1.1068 H R⁷ and R⁸ form unit ═NOCH₂CH₃ H H CH₃ 1.1069 CH₃ R⁷ and R⁸ form unit ═NOCH₂CH₃ H H H 1.1070 CH₃ R⁷ and R⁸ form unit ═NOCH₂CH₃ H H CH₃ 1.1071 H H H —O—(CH₂)₂—O— H 1.1072 H H H —O—(CH₂)₂—O— CH₃ 1.1073 CH₃ H H —O—(CH₂)₂—O— H 1.1074 CH₃ H H —O—(CH₂)₂—O— CH₃ 1.1075 H H H —O—(CH₂)₃—O— H 1.1076 H H H —O—(CH₂)₃—O— CH₃ 1.1077 CH₃ H H —O—(CH₂)₃—O— H 1.1078 CH₃ H H —O—(CH₂)₃—O— CH₃

Table 2 covers compounds of formula (A), wherein R¹ is ethyl, R² and R⁴ are methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 3 covers compounds of formula (A), wherein R¹ and R⁴ are ethyl, R² is methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 4 covers compounds of formula (A), wherein R¹, R² and R⁴ are ethyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 5 covers compounds of formula (A), wherein R¹ and R² are methyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 6 covers compounds of formula (A), wherein R¹ and R² are methyl, R⁴ is methoxy, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 7 covers compounds of formula (A), wherein R¹ and R² are methyl, R⁴ is chlorine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 8 covers compounds of formula (A), wherein R¹ and R² are methyl, R⁴ is bromine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 9 covers compounds of formula (A), wherein R¹ and R² are methyl, R⁴ is iodine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 10 covers compounds of formula (A), wherein R¹ and R² are methyl, R⁴ is ethynyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 11 covers compounds of formula (A), wherein R¹ and R² are methyl, R⁴ is vinyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 12 covers compounds of formula (A), wherein R¹ is ethyl, R² is methyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 13 covers compounds of formula (A), wherein R¹ is ethyl, R² is methyl, R⁴ is methoxy, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 14 covers compounds of formula (A), wherein R¹ is ethyl, R² is methyl, R⁴ is chlorine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 15 covers compounds of formula (A), wherein R¹ is ethyl, R² is methyl, R⁴ is bromine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 16 covers compounds of formula (A), wherein R¹ is ethyl, R² is methyl, R⁴ is iodine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 17 covers compounds of formula (A), wherein R¹ is ethyl, R² is methyl, R⁴ is ethynyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 18 covers compounds of formula (A), wherein R¹ is ethyl, R² is methyl, R⁴ is vinyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 19 covers compounds of formula (A), wherein R¹ is ethynyl, R² is methyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 20 covers compounds of formula (A), wherein R¹ is ethynyl, R² is methyl, R⁴ is methoxy, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 21 covers compounds of formula (A), wherein R¹ is ethynyl, R² is methyl, R⁴ is chlorine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 22 covers compounds of formula (A), wherein R¹ is ethynyl, R² is methyl, R⁴ is bromine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 23 covers compounds of formula (A), wherein R¹ is ethynyl, R² is methyl, R⁴ is iodine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 24 covers compounds of formula (A), wherein R¹ and R⁴ are ethynyl, R² is methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 25 covers compounds of formula (A), wherein R¹ is vinyl, R² is methyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 26 covers compounds of formula (A), wherein R¹ is vinyl, R² is methyl, R⁴ is methoxy, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 27 covers compounds of formula (A), wherein R¹ is vinyl, R² is methyl, R⁴ is chlorine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 28 covers compounds of formula (A), wherein R¹ is vinyl, R² is methyl, R⁴ is bromine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 29 covers compounds of formula (A), wherein R¹ is vinyl, R² is methyl, R⁴ is iodine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 30 covers compounds of formula (A), wherein R¹ and R⁴ are vinyl, R² is methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 31 covers compounds of formula (A), wherein R¹ is methyl, R², R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 32 covers compounds of formula (A), wherein R¹ is methyl, R² is methoxy, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 33 covers compounds of formula (A), wherein R¹ is methyl, R² is trifluoromethyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 34 covers compounds of formula (A), wherein R¹ is methyl, R² is ethyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 35 covers compounds of formula (A), wherein R¹ is methyl, R² is ethynyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 36 covers compounds of formula (A), wherein R¹ is methyl, R² is vinyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 37 covers compounds of formula (A), wherein R¹ is methyl, R² is chlorine, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 38 covers compounds of formula (A), wherein R¹ is methyl, R² is bromine, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 39 covers compounds of formula (A), wherein R¹ is methyl, R² is iodine, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 40 covers compounds of formula (A), wherein R¹ is ethyl, R², R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 41 covers compounds of formula (A), wherein R¹ is ethyl, R² is methoxy, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 42 covers compounds of formula (A), wherein R¹ is ethyl, R² is trifluoromethyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 43 covers compounds of formula (A), wherein R¹ is ethyl, R² is methyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 44 covers compounds of formula (A), wherein R¹ is ethyl, R² is ethynyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 45 covers compounds of formula (A), wherein R¹ is ethyl, R² is vinyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 46 covers compounds of formula (A), wherein R¹ is ethyl, R² is chlorine, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 47 covers compounds of formula (A), wherein R¹ is ethyl, R² is bromine, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 48 covers compounds of formula (A), wherein R¹ is ethyl, R² is iodine, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 49 covers compounds of formula (A), wherein R¹ and R⁴ are methyl, R² is chlorine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 50 covers compounds of formula (A), wherein R¹ and R⁴ are methyl, R² is bromine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 51 covers compounds of formula (A), wherein R¹ and R⁴ are methyl, R² is iodine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 52 covers compounds of formula (A), wherein R¹ is methyl, R² is chlorine, R³ is hydrogen, R⁴ is ethyl, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 53 covers compounds of formula (A), wherein R¹ is methyl, R² is bromine, R³ is hydrogen, R⁴ is ethyl, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 54 covers compounds of formula (A), wherein R¹ is methyl, R² is iodine, R³ is hydrogen, R⁴ is ethyl, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 55 covers compounds of formula (A), wherein R¹ and R⁴ are ethyl, R² is chlorine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 56 covers compounds of formula (A), wherein R¹ and R⁴ are ethyl, R² is bromine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 57 covers compounds of formula (A), wherein R¹ and R⁴ are ethyl, R² is iodine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 58 covers compounds of formula (A), wherein R¹ is methyl, R² is chlorine, R³ is hydrogen, R⁴ is methoxy, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 59 covers compounds of formula (A), wherein R¹ is methyl, R² is bromine, R³ is hydrogen, R⁴ is methoxy, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 60 covers compounds of formula (A), wherein R¹ is ethyl, R² is chlorine, R³ is hydrogen, R⁴ is methoxy, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 61 covers compounds of formula (A), wherein R¹ is ethyl, R² is bromine, R³ is hydrogen, R⁴ is methoxy, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 62 covers compounds of formula (A), wherein R¹ and R⁴ are methyl, R² is methoxy, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 63 covers compounds of formula (A), wherein R¹ is methyl, R² is methoxy, R³ is hydrogen, R⁴ is ethyl, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 64 covers compounds of formula (A), wherein R¹ and R⁴ are ethyl, R² is methoxy, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 65 covers compounds of formula (A), wherein R¹, R², R³ and R⁴ are methyl, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 66 covers compounds of formula (A), wherein R¹ is difluoromethoxy, R² and R⁴ are methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 67 covers compounds of formula (A), wherein R¹ is difluoromethoxy, R² is methyl, R⁴ is ethyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 68 covers compounds of formula (A), wherein R¹ is trifluoromethoxy, R² and R⁴ are methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 67 covers compounds of formula (A), wherein R¹ is trifluoromethoxy, R² is methyl, R⁴ is ethyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 70 covers compounds of formula (A), wherein R¹ is cyclopropyl, R² and R⁴ are methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 71 covers compounds of formula (A), wherein R¹ is cyclopropyl, R² is methyl, R⁴ is ethyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 72 covers compounds of formula (A), wherein R¹ and R² are methyl, R³, R⁵ and R¹² are hydrogen, R⁴ is cyclopropyl and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 73 covers compounds of formula (A), wherein R¹ and R² are ethyl, R³, R⁵ and R¹² are hydrogen, R⁴ is cyclopropyl and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined in Table 1.

Table 74 covers compounds of formula (AH)

wherein R¹, R² and R⁴ are methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

TABLE 74 R⁶ R⁸ R⁹ R¹¹ 74.001 H H H H 74.002 H H H CH₃ 74.003 H H H CH₂OH 74.004 H H H CH₂OCH₃ 74.005 H H H CH₂OCH₂CH₃ 74.006 H H H CH₂OCH₂OCH₃ 74.007 H H H CH₂OCH₂OCH₂CH₃ 74.007 H H H CH₂OCH₂CO₂CH₃ 74.008 H H H CH₂OCH₂CO₂CH₂CH₃ 74.009 H H H CH₂OCH₂CN 74.010 H H H CH(OH)CH₃ 74.011 H H H CH(CH₃)OCH₃ 74.012 H H H CH(CH₃)OCH₂CH₃ 74.013 H H H CHO 74.014 H H H COCH₃ 74.015 H H H CH₂COCH₃ 74.016 H H H CH₂CH₂COCH₃ 74.017 H H H CO₂H 74.018 H H H CO₂CH₃ 74.019 H H H CO₂CH₂CH₃ 74.020 H H H CH₂CO₂CH₃ 74.021 H H H CH₂CO₂CH₂CH₃ 74.022 H H H CH₂CH₂CO₂CH₃ 74.023 H H H CH₂CH₂CO₂CH₂CH₃ 74.024 H H H CONH₂ 74.025 H H H CONHCH₃ 74.026 H H H CONHCH₂CH₃ 74.027 H H H CON(CH₃)₂ 74.028 H H H CON(CH₂CH₃)₂ 74.029 H H H CON(CH₃)OCH₃ 74.030 H H H CH═NOH 74.031 H H H CH═NOCH₃ 74.032 H H H CH═NOCH₂CH₃ 74.033 H H H C(CH₃)═NOH 74.034 H H H C(CH₃)═NOCH₃ 74.035 H H H CH₂OC(O)CH₃ 74.036 H H H CH₂OC(O)CH₂CH₃ 74.037 H H H CH₂OC(O)CH(CH₃)₂ 74.038 H H H CH₂OC(O)C(CH₃)₃ 74.039 H H H CH₂OC(O)NHCH₃ 74.040 H H H CH₂OC(O)NHCH₂CH₃ 74.041 H H H CH₂OC(O)NHCH₂CH₂CH₃ 74.042 H H H CH₂OC(O)NHC(CH₃)₃ 74.043 H H H CH₂NH₂ 74.044 H H H CH₂NHCHO 74.045 H H H CH₂NHC(O)CH₃ 74.046 H H H CH₂NHC(O)OCH₃ 74.047 H H H NHCO₂CH₃ 74.048 H H H NHCO₂C(CH₃)₃ 74.049 H H H CN 74.050 H H H CH₂SCH₃ 74.051 H H H CH₂SCH₂CH₃ 74.052 H H H CH₂SCH₂CH₂CH₃ 74.053 H H H CH₂SCH(CH₃)₂ 74.054 H H H CH₂S(O)CH₃ 74.055 H H H CH₂SO₂CH₃ 74.056 H H H CH₂SCH₂CH₃ 74.057 H H H CH₂S(O)CH₂CH₃ 74.058 H H H CH₂SO₂CH₂CH₃ 74.059 H H H OCH₃ 74.060 H H H OCH₂CH₃ 74.061 H H H CH(OCH₃)₂ 74.062 H H H CH(OCH₂CH₃)₂ 74.063 H H H 1,3-dioxolan-2-yl 74.064 H H H 1,3-dioxan-2-yl 74.065 H H H 5,5-dimethyl-1,3-dioxan-2-yl 74.066 H H H CH₂CH₃ 74.067 H H H n-propyl 74.068 H H H isopropyl 74.069 H H H n-butyl 74.070 H H H isobutyl 74.071 H H H sec-butyl 74.072 H H H tert-butyl 74.073 H H H n-pentyl 74.074 H H H neopentyl 74.075 H H H n-hexyl 74.076 H H H n-heptyl 74.077 H H H CH₂CN 74.078 H H H cyclopropyl 74.079 H H H cyclobutyl 74.080 H H H cyclopentyl 74.081 H H H cyclohexyl 74.082 H H H CH₂-cyclopropyl 74.083 H H H benzyl 74.084 H H H CH₂CF₃ 74.085 H H H CH₂F 74.086 H H H CHF₂ 74.087 H H H CF₃ 74.088 H H CH₃ H 74.089 H H CH₂CH₃ H 74.090 H H n-propyl H 74.091 H H isopropyl H 74.092 H H n-butyl H 74.093 H H isobutyl H 74.094 H H sec-butyl H 74.095 H H tert-butyl H 74.096 H H vinyl H 74.097 H H ethynyl H 74.098 H H trimethylsilylethynyl H 74.099 H H CH₂OH H 74.100 H H CH₂OCH₃ H 74.101 H H CH₂OCH₂CH₃ H 74.102 H H CH₂OCH₂OCH₃ H 74.103 H H CH₂OCH₂OCH₂CH₃ H 74.104 H H CH₂OCH₂CH₂OCH₃ H 74.105 H H CHO H 74.106 H H COCH₃ H 74.107 H H CO₂H H 74.108 H H CO₂CH₃ H 74.109 H H CO₂CH₂CH₃ H 74.110 H H CONH₂ H 74.111 H H CONHCH₃ H 74.112 H H CONHCH₂CH₃ H 74.113 H H CON(CH₃)₂ H 74.114 H H CON(CH₂—CH₃)₂ H 74.115 H H CON(CH₃)OCH₃ H 74.116 H H CH═NOH H 74.117 H H CH═N—OCH₃ H 74.118 H H CH═N—OCH₂CH₃ H 74.119 H H C(CH₃)═N—OH H 74.120 H H C(CH₃)═N—OCH₃ H 74.121 H H CH₂OC(O)—NHCH₃ H 74.122 H H CH₂NH₂ H 74.123 H H CH₂NHCHO H 74.124 H H CH₂NHC(O)CH₃ H 74.125 H H CH₂NHC(O)OCH₃ H 74.126 H H CH(OH)CH₃ H 74.127 H H CH(CH₃)OCH₃ H 74.128 H H CN H 74.129 H H CH₂SCH₃ H 74.130 H H CH₂S(O)CH₃ H 74.131 H H CH₂SO₂CH₃ H 74.132 H H CH₂SCH₂CH₃ H 74.133 H H CH₂S(O)CH₂CH₃ H 74.134 H H CH₂SO₂CH₂CH₃ H 74.135 H H OCH₃ H 74.136 H H OCH₂CH₃ H 74.137 H H CH(OCH₃)₂ H 74.138 H H CH(OCH₂CH₃)₂ H 74.139 H H cyclopropyl H 74.140 H H cyclobutyl H 74.141 H H cyclopentyl H 74.142 H H cyclohexyl H 74.143 H H F H 74.144 H H Cl H 74.145 H H Br H 74.146 H H I H 74.147 H H phenyl H 74.148 H H 2-acetylphenyl H 74.149 H H 3-acetylphenyl H 74.150 H H 4-acetylphenyl H 74.151 H H 2-chlorophenyl H 74.152 H H 3-chlorophenyl H 74.153 H H 4-chlorophenyl H 74.154 H H 2-cyanophenyl H 74.155 H H 3-cyanophenyl H 74.156 H H 4-cyanophenyl H 74.157 H H 2-fluorophenyl H 74.158 H H 3-fluorophenyl H 74.159 H H 4-fluorophenyl H 74.160 H H 2-methoxyphenyl H 74.161 H H 3-methoxyphenyl H 74.162 H H 4-methoxyphenyl H 74.163 H H 2-methylphenyl H 74.164 H H 3-methylphenyl H 74.165 H H 4-methylphenyl H 74.166 H H 2-nitrophenyl H 74.167 H H 3-nitrophenyl H 74.168 H H 4-nitrophenyl H 74.169 H H 2-thiomethylphenyl H 74.170 H H 3-thiomethylphenyl H 74.171 H H 4-thiomethylphenyl H 74.172 H H 2-trifluoromethoxyphenyl H 74.173 H H 3-trifluoromethoxyphenyl H 74.174 H H 4-trifluoromethoxyphenyl H 74.175 H H 2-trifluoromethylphenyl H 74.176 H H 3-trifluoromethylphenyl H 74.177 H H 4-trifluoromethylphenyl H 74.178 H H 2,3-dichlorophenyl H 74.179 H H 2,4-dichlorophenyl H 74.180 H H 2,5-dichlorophenyl H 74.181 H H 2,6-dichlorophenyl H 74.182 H H 3,4-dichlorophenyl H 74.183 H H 3,5-dichlorophenyl H 74.184 H H 2,3-difluorophenyl H 74.185 H H 2,4-difluorophenyl H 74.186 H H 2,5-difluorophenyl H 74.187 H H 2,6-difluorophenyl H 74.188 H H 3,4-difluorophenyl H 74.189 H H 3,5-difluorophenyl H 74.190 H H 2,4,6-trifluorophenyl H 74.191 H H 2,4-dimethylphenyl H 74.192 H H 2,4,6-trimethylphenyl H 74.193 H H 3,4,5-trimethoxyphenyl H 74.194 H H 2-chloro-3-cyanophenyl H 74.195 H H 2-chloro-4-cyanophenyl H 74.196 H H 2-chloro-5-cyanophenyl h 74.197 H H 2-chloro-6-cyanophenyl H 74.198 H H 3-chloro-2-cyanophenyl H 74.199 H H 3-chloro-4-cyanophenyl H 74.200 H H 3-chloro-5-cyanophenyl H 74.201 H H 5-chloro-2-cyanophenyl H 74.202 H H 4-chloro-2-cyanophenyl H 74.203 H H 4-chloro-3-cyanophenyl H 74.204 H H 2-chloro-3-fluorophenyl H 74.205 H H 2-chloro-4-fluorophenyl H 74.206 H H 2-chloro-5-fluorophenyl H 74.207 H H 2-chloro-6-fluorophenyl H 74.208 H H 3-chloro-2-fluorophenyl H 74.209 H H 3-chloro-4-fluorophenyl H 74.210 H H 3-chloro-5-fluorophenyl H 74.211 H H 5-chloro-2-fluorophenyl H 74.212 H H 4-chloro-2-fluorophenyl H 74.213 H H 4-chloro-3-fluorophenyl H 74.214 H H 2-chloro-3-methylphenyl H 74.215 H H 2-chloro-4-methylphenyl H 74.216 H H 2-chloro-5-methylphenyl H 74.217 H H 2-chloro-6-methylphenyl H 74.218 H H 3-chloro-2-methylphenyl H 74.219 H H 3-chloro-4-methylphenyl H 74.220 H H 3-chloro-5-methylphenyl H 74.221 H H 5-chloro-2-methylphenyl H 74.222 H H 4-chloro-2-methylphenyl H 74.223 H H 4-chloro-3-methylphenyl H 74.224 H H 2-cyano-3-fluorophenyl H 74.225 H H 2-cyano-4-fluorophenyl H 74.226 H H 2-cyano-5-fluorophenyl H 74.227 H H 2-cyano-6-fluorophenyl H 74.228 H H 3-cyano-2-fluorophenyl H 74.229 H H 3-cyano-4-fluorophenyl H 74.230 H H 3-cyano-5-fluorophenyl H 74.231 H H 5-cyano-2-fluorophenyl H 74.232 H H 4-cyano-2-fluorophenyl H 74.233 H H 4-cyano-3-fluorophenyl H 74.234 H H 2-fluoro-3-methylphenyl H 74.235 H H 2-fluoro-4-methylphenyl H 74.236 H H 2-fluoro-5-methylphenyl H 74.237 H H 2-fluoro-6-methylphenyl H 74.238 H H 3-fluoro-2-methylphenyl H 74.239 H H 3-fluoro-4-methylphenyl H 74.240 H H 3-fluoro-5-methylphenyl H 74.241 H H 5-fluoro-2-methylphenyl H 74.242 H H 4-fluoro-2-methylphenyl H 74.243 H H 4-fluoro-3-methylphenyl H 74.244 H H pyridin-2-yl H 74.245 H H pyridin-3-yl H 74.246 H H pyridin-4-yl H 74.247 H H 3-chloropyridin-2-yl H 74.248 H H 4-chloropyridin-2-yl H 74.249 H H 5-chloropyridin-2-yl H 74.250 H H 6-chloropyridin-2-yl H 74.251 H H 2-chloropyridin-3-yl H 74.252 H H 4-chloropyridin-3-yl H 74.253 H H 5-chloropyridin-3-yl H 74.254 H H 2-chloropyridin-4-yl H 74.255 H H 3-chloropyridin-4-yl H 74.256 H H 2-chloropyridin-5-yl H 74.257 H H 3-cyanopyridin-2-yl H 74.258 H H 4-cyanopyridin-2-yl H 74.259 H H 5-cyanopyridin-2-yl H 74.260 H H 6-cyanopyridin-2-yl H 74.261 H H 2-cyanopyridin-3-yl H 74.262 H H 4-cyanopyridin-3-yl H 74.263 H H 5-cyanopyridin-3-yl H 74.264 H H 2-cyanopyridin-5-yl H 74.265 H H 3-fluoropyridin-2-yl H 74.266 H H 4-fluoropyridin-2-yl H 74.267 H H 5-fluoropyridin-2-yl H 74.268 H H 6-fluoropyridin-2-yl H 74.269 H H 2-fluoropyridin-3-yl H 74.270 H H 4-fluoropyridin-3-yl H 74.271 H H 5-fluoropyridin-3-yl H 74.272 H H 2-fluoropyridin-5-yl H 74.273 H H 3-nitropyridin-2-yl H 74.274 H H 4-nitropyridin-2-yl H 74.275 H H 5-nitropyridin-2-yl H 74.276 H H 6-nitropyridin-2-yl H 74.277 H H 2-nitropyridin-3-yl H 74.278 H H 4-nitropyridin-3-yl H 74.279 H H 5-nitropyridin-3-yl H 74.280 H H 2-nitropyridin-5-yl H 74.281 H H 3-trifluoromethylpyridin-2-yl H 74.282 H H 4-trifluoromethylpyridin-2-yl H 74.283 H H 5-trifluoromethylpyridin-2-yl H 74.284 H H 6-trifluoromethylpyridin-2-yl H 74.285 H H 2-trifluoromethylpyridin-3-yl H 74.286 H H 4-trifluoromethylpyridin-3-yl H 74.287 H H 5-trifluoromethylpyridin-3-yl H 74.288 H H 2-trifluoromethylpyridin-5-yl H 74.289 H H 2,6-bis(trifluoromethyl)pyridin-3-yl H 74.290 H H 2,6-bis(trifluoromethyl)pyridin-4-yl H 74.291 H H 3,5-bis(trifluoromethyl)pyridin-2-yl H 74.292 H H 2-thienyl H 74.293 H H 3-thienyl H 74.294 H H 5-cyanothien-2-yl H 74.295 H H 2-furyl H 74.296 H H 3-furyl H 74.297 H H 1-methyl-1,2,3-triazol-4-yl H 74.298 H H 2-methylthiopyrimidin-4-yl H 74.299 H H 5-methyl-2-methylthiopyrimidin-4-yl H 74.300 H H pyrazin-2-yl H 74.301 H H 3,6-dimethylpyrazin-2-yl H 74.302 H H 3-cyanopyrazin-2-yl H 74.303 H H quinolin-2-yl H 74.304 H H 3-ethylquinolin-2-yl H 74.305 H H benzyl H 74.306 H H 4-fluorobenzyl H 74.307 H H 4-chlorobenzyl H 74.308 H H 4-methylbenzyl H 74.309 H H 2,4-dimethylbenzyl H 74.310 H H 2,4,6-trimethylbenzyl H 74.311 H H CH₃ CH₃ 74.312 H H CH₂CH₃ CH₃ 74.313 H H n-propyl CH₃ 74.314 H H isopropyl CH₃ 74.315 H H n-butyl CH₃ 74.316 H H isobutyl CH₃ 74.317 H H sec-butyl CH₃ 74.318 H H tert-butyl CH₃ 74.319 H H vinyl CH₃ 74.320 H H ethynyl CH₃ 74.321 H H trimethylsilylethynyl CH₃ 74.322 H H CH₂OH CH₃ 74.323 H H CH₂OCH₃ CH₃ 74.324 H H CH₂OCH₂CH₃ CH₃ 74.325 H H CH₂OCH₂OCH₃ CH₃ 74.326 H H CH₂OCH₂OCH₂CH₃ CH₃ 74.327 H H CH₂OCH₂CH₂OCH₃ CH₃ 74.328 H H CHO CH₃ 74.329 H H COCH₃ CH₃ 74.330 H H CO₂H CH₃ 74.331 H H CO₂CH₃ CH₃ 74.332 H H CO₂CH₂CH₃ CH₃ 74.333 H H CONH₂ CH₃ 74.334 H H CONHCH₃ CH₃ 74.335 H H CONHCH₂CH₃ CH₃ 74.336 H H CON(CH₃)₂ CH₃ 74.337 H H CON(CH₂—CH₃)₂ CH₃ 74.338 H H CON(CH₃)OCH₃ CH₃ 74.339 H H CH═NOH CH₃ 74.340 H H CH═N—OCH₃ CH₃ 74.341 H H CH═N—OCH₂CH₃ CH₃ 74.342 H H C(CH₃)═N—OH CH₃ 74.343 H H C(CH₃)═N—OCH₃ CH₃ 74.344 H H CH₂OC(O)—NHCH₃ CH₃ 74.345 H H CH₂NH₂ CH₃ 74.346 H H CH₂NHCHO CH₃ 74.347 H H CH₂NHC(O)CH₃ CH₃ 74.348 H H CH₂NHC(O)OCH₃ CH₃ 74.349 H H CH(OH)CH₃ CH₃ 74.350 H H CH(CH₃)OCH₃ CH₃ 74.351 H H CN CH₃ 74.352 H H CH₂SCH₃ CH₃ 74.353 H H CH₂S(O)CH₃ CH₃ 74.354 H H CH₂SO₂CH₃ CH₃ 74.355 H H CH₂SCH₂CH₃ CH₃ 74.356 H H CH₂S(O)CH₂CH₃ CH₃ 74.357 H H CH₂SO₂CH₂CH₃ CH₃ 74.358 H H OCH₃ CH₃ 74.359 H H OCH₂CH₃ CH₃ 74.360 H H CH(OCH₃)₂ CH₃ 74.361 H H CH(OCH₂CH₃)₂ CH₃ 74.362 H H cyclopropyl CH₃ 74.363 H H cyclobutyl CH₃ 74.364 H H cyclopentyl CH₃ 74.365 H H cyclohexyl CH₃ 74.366 H H F CH₃ 74.367 H H Cl CH₃ 74.368 H H Br CH₃ 74.369 H H I CH₃ 74.370 H H phenyl CH₃ 74.371 H H 2-acetylphenyl CH₃ 74.372 H H 3-acetylphenyl CH₃ 74.373 H H 4-acetylphenyl CH₃ 74.374 H H 2-chlorophenyl CH₃ 74.375 H H 3-chlorophenyl CH₃ 74.376 H H 4-chlorophenyl CH₃ 74.377 H H 2-cyanophenyl CH₃ 74.378 H H 3-cyanophenyl CH₃ 74.379 H H 4-cyanophenyl CH₃ 74.380 H H 2-fluorophenyl CH₃ 74.381 H H 3-fluorophenyl CH₃ 74.382 H H 4-fluorophenyl CH₃ 74.383 H H 2-methoxyphenyl CH₃ 74.384 H H 3-methoxyphenyl CH₃ 74.385 H H 4-methoxyphenyl CH₃ 74.386 H H 2-methylphenyl CH₃ 74.387 H H 3-methylphenyl CH₃ 74.388 H H 4-methylphenyl CH₃ 74.389 H H 2-nitrophenyl CH₃ 74.390 H H 3-nitrophenyl CH₃ 74.391 H H 4-nitrophenyl CH₃ 74.392 H H 2-thiomethylphenyl CH₃ 74.393 H H 3-thiomethylphenyl CH₃ 74.394 H H 4-thiomethylphenyl CH₃ 74.395 H H 2-trifluoromethoxyphenyl CH₃ 74.396 H H 3-trifluoromethoxyphenyl CH₃ 74.397 H H 4-trifluoromethoxyphenyl CH₃ 74.398 H H 2-trifluoromethylphenyl CH₃ 74.399 H H 3-trifluoromethylphenyl CH₃ 74.400 H H 4-trifluoromethylphenyl CH₃ 74.401 H H 2,3-dichlorophenyl CH₃ 74.402 H H 2,4-dichlorophenyl CH₃ 74.403 H H 2,5-dichlorophenyl CH₃ 74.404 H H 2,6-dichlorophenyl CH₃ 74.405 H H 3,4-dichlorophenyl CH₃ 74.406 H H 3,5-dichlorophenyl CH₃ 74.407 H H 2,3-difluorophenyl CH₃ 74.408 H H 2,4-difluorophenyl CH₃ 74.409 H H 2,5-difluorophenyl CH₃ 74.410 H H 2,6-difluorophenyl CH₃ 74.411 H H 3,4-difluorophenyl CH₃ 74.412 H H 3,5-difluorophenyl CH₃ 74.413 H H 2,4,6-trifluorophenyl CH₃ 74.414 H H 2,4-dimethylphenyl CH₃ 74.415 H H 2,4,6-trimethylphenyl CH₃ 74.416 H H 3,4,5-trimethoxyphenyl CH₃ 74.417 H H 2-chloro-3-cyanophenyl CH₃ 74.418 H H 2-chloro-4-cyanophenyl CH₃ 74.419 H H 2-chloro-5-cyanophenyl CH₃ 74.420 H H 2-chloro-6-cyanophenyl CH₃ 74.421 H H 3-chloro-2-cyanophenyl CH₃ 74.422 H H 3-chloro-4-cyanophenyl CH₃ 74.423 H H 3-chloro-5-cyanophenyl CH₃ 74.424 H H 5-chloro-2-cyanophenyl CH₃ 74.425 H H 4-chloro-2-cyanophenyl CH₃ 74.426 H H 4-chloro-3-cyano-phenyl CH₃ 74.427 H H 2-chloro-3-fluorophenyl CH₃ 74.428 H H 2-chloro-4-fluorophenyl CH₃ 74.429 H H 2-chloro-5-fluoro-phenyl CH₃ 74.430 H H 2-chloro-6-fluorophenyl CH₃ 74.431 H H 3-chloro-2-fluorophenyl CH₃ 74.432 H H 3-chloro-4-fluorophenyl CH₃ 74.433 H H 3-chloro-5-fluorophenyl CH₃ 74.434 H H 5-chloro-2-fluorophenyl CH₃ 74.435 H H 4-chloro-2-fluorophenyl CH₃ 74.436 H H 4-chloro-3-fluorophenyl CH₃ 74.437 H H 2-chloro-3-methylphenyl CH₃ 74.438 H H 2-chloro-4-methyl phenyl CH₃ 74.439 H H 2-chloro-5-methylphenyl CH₃ 74.440 H H 2-chloro-6-methylphenyl CH₃ 74.441 H H 3-chloro-2-methylphenyl CH₃ 74.442 H H 3-chloro-4-methylphenyl CH₃ 74.443 H H 3-chloro-5-methylphenyl CH₃ 74.444 H H 5-chloro-2-methylphenyl CH₃ 74.445 H H 4-chloro-2-methylphenyl CH₃ 74.446 H H 4-chloro-3-methyl phenyl CH₃ 74.447 H H 2-cyano-3-fluorophenyl CH₃ 74.448 H H 2-cyano-4-fluorophenyl CH₃ 74.449 H H 2-cyano-5-fluorophenyl CH₃ 74.450 H H 2-cyano-6-fluorophenyl CH₃ 74.451 H H 3-cyano-2-fluorophenyl CH₃ 74.452 H H 3-cyano-4-fluorophenyl CH₃ 74.453 H H 3-cyano-5-fluorophenyl CH₃ 74.454 H H 5-cyano-2-fluorophenyl CH₃ 74.455 H H 4-cyano-2-fluorophenyl CH₃ 74.456 H H 4-cyano-3-fluorophenyl CH₃ 74.457 H H 2-fluoro-3-methylphenyl CH₃ 74.458 H H 2-fluoro-4-methylphenyl CH₃ 74.459 H H 2-fluoro-5-methylphenyl CH₃ 74.460 H H 2-fluoro-6-methylphenyl CH₃ 74.461 H H 3-fluoro-2-methylphenyl CH₃ 74.462 H H 3-fluoro-4-methylphenyl CH₃ 74.463 H H 3-fluoro-5-methylphenyl CH₃ 74.464 H H 5-fluoro-2-methylphenyl CH₃ 74.465 H H 4-fluoro-2-methylphenyl CH₃ 74.466 H H 4-fluoro-3-methylphenyl CH₃ 74.467 H H pyridin-2-yl CH₃ 74.468 H H pyridin-3-yl CH₃ 74.469 H H pyridin-4-yl CH₃ 74.470 H H 3-chloropyridin-2-yl CH₃ 74.471 H H 4-chloropyridin-2-yl CH₃ 74.472 H H 5-chloropyridin-2-yl CH₃ 74.473 H H 6-chloropyridin-2-yl CH₃ 74.474 H H 2-chloropyridin-3-yl CH₃ 74.475 H H 4-chloropyridin-3-yl CH₃ 74.476 H H 5-chloropyridin-3-yl CH₃ 74.477 H H 2-chloropyridin-4-yl CH₃ 74.478 H H 3-chloropyridin-4-yl CH₃ 74.479 H H 2-chloropyridin-5-yl CH₃ 74.480 H H 3-cyanopyridin-2-yl CH₃ 74.481 H H 4-cyanopyridin-2-yl CH₃ 74.482 H H 5-cyanopyridin-2-yl CH₃ 74.483 H H 6-cyanopyridin-2-yl CH₃ 74.484 H H 2-cyanopyridin-3-yl CH₃ 74.485 H H 4-cyanopyridin-3-yl CH₃ 74.486 H H 5-cyanopyridin-3-yl CH₃ 74.487 H H 2-cyanopyridin-5-yl CH₃ 74.488 H H 3-fluoropyridin-2-yl CH₃ 74.489 H H 4-fluoropyridin-2-yl CH₃ 74.490 H H 5-fluoropyridin-2-yl CH₃ 74.491 H H 6-fluoropyridin-2-yl CH₃ 74.492 H H 2-fluoropyridin-3-yl CH₃ 74.493 H H 4-fluoropyridin-3-yl CH₃ 74.494 H H 5-fluoropyridin-3-yl CH₃ 74.495 H H 2-fluoropyridin-5-yl CH₃ 74.496 H H 3-nitropyridin-2-yl CH₃ 74.497 H H 4-nitropyridin-2-yl CH₃ 74.498 H H 5-nitropyridin-2-yl CH₃ 74.499 H H 6-nitropyridin-2-yl CH₃ 74.500 H H 2-nitropyridin-3-yl CH₃ 74.501 H H 4-nitropyridin-3-yl CH₃ 74.502 H H 5-nitropyridin-3-yl CH₃ 74.503 H H 2-nitropyridin-5-yl CH₃ 74.504 H H 3-trifluoromethylpyridin-2-yl CH₃ 74.505 H H 4-trifluoromethylpyridin-2-yl CH₃ 74.506 H H 5-trifluoromethylpyridin-2-yl CH₃ 74.507 H H 6-trifluoromethylpyridin-2-yl CH₃ 74.508 H H 2-trifluoromethylpyridin-3-yl CH₃ 74.509 H H 4-trifluoromethylpyridin-3-yl CH₃ 74.510 H H 5-trifluoromethylpyridin-3-yl CH₃ 74.511 H H 2-trifluoromethylpyridin-5-yl CH₃ 74.512 H H 2,6-bis(trifluoromethyl)pyridin-3-yl CH₃ 74.513 H H 2,6-bis(trifluoromethyl)pyridin-4-yl CH₃ 74.514 H H 3,5-bis(trifluoromethyl)pyridin-2-yl CH₃ 74.515 H H 2-thienyl CH₃ 74.516 H H 3-thienyl CH₃ 74.517 H H 5-cyanothien-2-yl CH₃ 74.518 H H 2-furyl CH₃ 74.519 H H 3-furyl CH₃ 74.520 H H 1-methyl-1,2,3-triazol-4-yl CH₃ 74.521 H H 2-methylthiopyrimidin-4-yl CH₃ 74.522 H H 5-methyl-2-methylthiopyrimidin-4-yl CH₃ 74.523 H H pyrazin-2-yl CH₃ 74.524 H H 3,6-dimethylpyrazin-2-yl CH₃ 74.525 H H 3-cyanopyrazin-2-yl CH₃ 74.526 H H quinolin-2-yl CH₃ 74.527 H H 3-ethylquinolin-2-yl CH₃ 74.528 H H benzyl CH₃ 74.529 H H 4-fluorobenzyl CH₃ 74.530 H H 4-chlorobenzyl CH₃ 74.531 H H 4-methylbenzyl CH₃ 74.532 H H 2,4-dimethylbenzyl CH₃ 74.533 H H 2,4,6-trimethylbenzyl CH₃ 74.534 CH₃ H CH₃ H 74.535 CH₃ H CH₂CH₃ H 74.536 CH₃ H n-propyl H 74.537 CH₃ H isopropyl H 74.538 CH₃ H n-butyl H 74.539 CH₃ H isobutyl H 74.540 CH₃ H sec-butyl H 74.541 CH₃ H tert-butyl H 74.542 CH₃ H vinyl H 74.543 CH₃ H ethynyl H 74.544 CH₃ H trimethylsilylethynyl H 74.545 CH₃ H CH₂OH H 74.546 CH₃ H CH₂OCH₃ H 74.547 CH₃ H CH₂OCH₂CH₃ H 74.548 CH₃ H CH₂OCH₂OCH₃ H 74.549 CH₃ H CH₂OCH₂OCH₂CH₃ H 74.550 CH₃ H CH₂OCH₂CH₂OCH₃ H 74.551 CH₃ H CHO H 74.552 CH₃ H COCH₃ H 74.553 CH₃ H CO₂H H 74.554 CH₃ H CO₂CH₃ H 74.555 CH₃ H CO₂CH₂CH₃ H 74.556 CH₃ H CONH₂ H 74.557 CH₃ H CONHCH₃ H 74.558 CH₃ H CONHCH₂CH₃ H 74.559 CH₃ H CON(CH₃)₂ H 74.560 CH₃ H CON(CH₂—CH₃)₂ H 74.561 CH₃ H CON(CH₃)OCH₃ H 74.562 CH₃ H CH═NOH H 74.563 CH₃ H CH═N—OCH₃ H 74.564 CH₃ H CH═N—OCH₂CH₃ H 74.565 CH₃ H C(CH₃)═N—OH H 74.566 CH₃ H C(CH₃)═N—OCH₃ H 74.567 CH₃ H CH₂OC(O)—NHCH₃ H 74.568 CH₃ H CH₂NH₂ H 74.569 CH₃ H CH₂NHCHO H 74.570 CH₃ H CH₂NHC(O)CH₃ H 74.571 CH₃ H CH₂NHC(O)OCH₃ H 74.572 CH₃ H CH(OH)CH₃ H 74.573 CH₃ H CH(CH₃)OCH₃ H 74.574 CH₃ H CN H 74.575 CH₃ H CH₂SCH₃ H 74.576 CH₃ H CH₂S(O)CH₃ H 74.577 CH₃ H CH₂SO₂CH₃ H 74.578 CH₃ H CH₂SCH₂CH₃ H 74.579 CH₃ H CH₂S(O)CH₂CH₃ H 74.580 CH₃ H CH₂SO₂CH₂CH₃ H 74.581 CH₃ H OCH₃ H 74.582 CH₃ H OCH₂CH₃ H 74.583 CH₃ H CH(OCH₃)₂ H 74.584 CH₃ H CH(OCH₂CH₃)₂ H 74.585 CH₃ H cyclopropyl H 74.586 CH₃ H cyclobutyl H 74.587 CH₃ H cyclopentyl H 74.588 CH₃ H cyclohexyl H 74.589 CH₃ H F H 74.590 CH₃ H Cl H 74.591 CH₃ H Br H 74.592 CH₃ H I H 74.593 CH₃ H phenyl H 74.594 CH₃ H 2-acetylphenyl H 74.595 CH₃ H 3-acetylphenyl H 74.596 CH₃ H 4-acetylphenyl H 74.597 CH₃ H 2-chlorophenyl H 74.598 CH₃ H 3-chlorophenyl H 74.599 CH₃ H 4-chlorophenyl H 74.600 CH₃ H 2-cyanophenyl H 74.601 CH₃ H 3-cyanophenyl H 74.602 CH₃ H 4-cyanophenyl H 74.603 CH₃ H 2-fluorophenyl H 74.604 CH₃ H 3-fluorophenyl H 74.605 CH₃ H 4-fluorophenyl H 74.606 CH₃ H 2-methoxyphenyl H 74.607 CH₃ H 3-methoxyphenyl H 74.608 CH₃ H 4-methoxyphenyl H 74.609 CH₃ H 2-methylphenyl H 74.610 CH₃ H 3-methylphenyl H 74.611 CH₃ H 4-methylphenyl H 74.612 CH₃ H 2-nitrophenyl H 74.613 CH₃ H 3-nitrophenyl H 74.614 CH₃ H 4-nitrophenyl H 74.615 CH₃ H 2-thiomethylphenyl H 74.616 CH₃ H 3-thiomethylphenyl H 74.617 CH₃ H 4-thiomethylphenyl H 74.618 CH₃ H 2-trifluoromethoxyphenyl H 74.619 CH₃ H 3-trifluoromethoxyphenyl H 74.620 CH₃ H 4-trifluoromethoxyphenyl H 74.621 CH₃ H 2-trifluoromethylphenyl H 74.622 CH₃ H 3-trifluoromethylphenyl H 74.623 CH₃ H 4-trifluoromethylphenyl H 74.624 CH₃ H 2,3-dichlorophenyl H 74.625 CH₃ H 2,4-dichlorophenyl H 74.626 CH₃ H 2,5-dichlorophenyl H 74.627 CH₃ H 2,6-dichlorophenyl H 74.628 CH₃ H 3,4-dichlorophenyl H 74.629 CH₃ H 3,5-dichlorophenyl H 74.630 CH₃ H 2,3-difluorophenyl H 74.631 CH₃ H 2,4-difluorophenyl H 74.632 CH₃ H 2,5-difluorophenyl H 74.633 CH₃ H 2,6-difluorophenyl H 74.634 CH₃ H 3,4-difluorophenyl H 74.635 CH₃ H 3,5-difluorophenyl H 74.636 CH₃ H 2,4,6-trifluorophenyl H 74.637 CH₃ H 2,4-dimethylphenyl H 74.638 CH₃ H 2,4,6-trimethylphenyl H 74.639 CH₃ H 3,4,5-trimethoxyphenyl H 74.640 CH₃ H 2-chloro-3-cyanophenyl H 74.641 CH₃ H 2-chloro-4-cyanophenyl H 74.642 CH₃ H 2-chloro-5-cyanophenyl H 74.643 CH₃ H 2-chloro-6-cyanophenyl H 74.644 CH₃ H 3-chloro-2-cyanophenyl H 74.645 CH₃ H 3-chloro-4-cyanophenyl H 74.646 CH₃ H 3-chloro-5-cyanophenyl H 74.647 CH₃ H 5-chloro-2-cyanophenyl H 74.648 CH₃ H 4-chloro-2-cyanophenyl H 74.649 CH₃ H 4-chloro-3-cyanophenyl H 74.650 CH₃ H 2-chloro-3-fluorophenyl H 74.651 CH₃ H 2-chloro-4-fluorophenyl H 74.652 CH₃ H 2-chloro-5-fluorophenyl H 74.653 CH₃ H 2-chloro-6-fluorophenyl H 74.654 CH₃ H 3-chloro-2-fluorophenyl H 74.655 CH₃ H 3-chloro-4-fluorophenyl H 74.656 CH₃ H 3-chloro-5-fluorophenyl H 74.657 CH₃ H 5-chloro-2-fluorophenyl H 74.658 CH₃ H 4-chloro-2-fluorophenyl H 74.659 CH₃ H 4-chloro-3-fluorophenyl H 74.660 CH₃ H 2-chloro-3-methylphenyl H 74.661 CH₃ H 2-chloro-4-methylphenyl H 74.662 CH₃ H 2-chloro-5-methylphenyl H 74.663 CH₃ H 2-chloro-6-methylphenyl H 74.664 CH₃ H 3-chloro-2-methylphenyl H 74.665 CH₃ H 3-chloro-4-methylphenyl H 74.666 CH₃ H 3-chloro-5-methylphenyl H 74.667 CH₃ H 5-chloro-2-methylphenyl H 74.668 CH₃ H 4-chloro-2-methylphenyl H 74.669 CH₃ H 4-chloro-3-methylphenyl H 74.670 CH₃ H 2-cyano-3-fluorophenyl H 74.671 CH₃ H 2-cyano-4-fluorophenyl H 74.672 CH₃ H 2-cyano-5-fluorophenyl H 74.673 CH₃ H 2-cyano-6-fluorophenyl H 74.674 CH₃ H 3-cyano-2-fluorophenyl H 74.675 CH₃ H 3-cyano-4-fluorophenyl H 74.676 CH₃ H 3-cyano-5-fluorophenyl H 74.677 CH₃ H 5-cyano-2-fluorophenyl H 74.678 CH₃ H 4-cyano-2-fluorophenyl H 74.679 CH₃ H 4-cyano-3-fluorophenyl H 74.680 CH₃ H 2-fluoro-3-methylphenyl H 74.681 CH₃ H 2-fluoro-4-methylphenyl H 74.682 CH₃ H 2-fluoro-5-methylphenyl H 74.683 CH₃ H 2-fluoro-6-methylphenyl H 74.684 CH₃ H 3-fluoro-2-methylphenyl H 74.685 CH₃ H 3-fluoro-4-methylphenyl H 74.686 CH₃ H 3-fluoro-5-methylphenyl H 74.687 CH₃ H 5-fluoro-2-methylphenyl H 74.688 CH₃ H 4-fluoro-2-methylphenyl H 74.689 CH₃ H 4-fluoro-3-methylphenyl H 74.690 CH₃ H pyridin-2-yl H 74.691 CH₃ H pyridin-3-yl H 74.692 CH₃ H pyridin-4-yl H 74.693 CH₃ H 3-chloropyridin-2-yl H 74.694 CH₃ H 4-chloropyridin-2-yl H 74.695 CH₃ H 5-chloropyridin-2-yl H 74.696 CH₃ H 6-chloropyridin-2-yl H 74.697 CH₃ H 2-chloropyridin-3-yl H 74.698 CH₃ H 4-chloropyridin-3-yl H 74.699 CH₃ H 5-chloropyridin-3-yl H 74.700 CH₃ H 2-chloropyridin-4-yl H 74.701 CH₃ H 3-chloropyridin-4-yl H 74.702 CH₃ H 2-chloropyridin-5-yl H 74.703 CH₃ H 3-cyanopyridin-2-yl H 74.704 CH₃ H 4-cyanopyridin-2-yl H 74.705 CH₃ H 5-cyanopyridin-2-yl H 74.706 CH₃ H 6-cyanopyridin-2-yl H 74.707 CH₃ H 2-cyanopyridin-3-yl H 74.708 CH₃ H 4-cyanopyridin-3-yl H 74.709 CH₃ H 5-cyanopyridin-3-yl H 74.710 CH₃ H 2-cyanopyridin-5-yl H 74.711 CH₃ H 3-fluoropyridin-2-yl H 74.712 CH₃ H 4-fluoropyridin-2-yl H 74.713 CH₃ H 5-fluoropyridin-2-yl H 74.714 CH₃ H 6-fluoropyridin-2-yl H 74.715 CH₃ H 2-fluoropyridin-3-yl H 74.716 CH₃ H 4-fluoropyridin-3-yl H 74.717 CH₃ H 5-fluoropyridin-3-yl H 74.718 CH₃ H 2-fluoropyridin-5-yl H 74.719 CH₃ H 3-nitropyridin-2-yl H 74.720 CH₃ H 4-nitropyridin-2-yl H 74.721 CH₃ H 5-nitropyridin-2-yl H 74.722 CH₃ H 6-nitropyridin-2-yl H 74.723 CH₃ H 2-nitropyridin-3-yl H 74.724 CH₃ H 4-nitropyridin-3-yl H 74.725 CH₃ H 5-nitropyridin-3-yl H 74.726 CH₃ H 2-nitropyridin-5-yl H 74.727 CH₃ H 3-trifluoromethylpyridin-2-yl H 74.728 CH₃ H 4-trifluoromethylpyridin-2-yl H 74.729 CH₃ H 5-trifluoromethylpyridin-2-yl H 74.730 CH₃ H 6-trifluoromethylpyridin-2-yl H 74.731 CH₃ H 2-trifluoromethylpyridin-3-yl H 74.732 CH₃ H 4-trifluoromethylpyridin-3-yl H 74.733 CH₃ H 5-trifluoromethylpyridin-3-yl H 74.734 CH₃ H 2-trifluoromethylpyridin-5-yl H 74.735 CH₃ H 2,6-bis(trifluoromethyl)pyridin-3-yl H 74.736 CH₃ H 2,6-bis(trifluoromethyl)pyridin-4-yl H 74.737 CH₃ H 3,5-bis(trifluoromethyl)pyridin-2-yl H 74.738 CH₃ H 2-thienyl H 74.739 CH₃ H 3-thienyl H 74.740 CH₃ H 5-cyanothien-2-yl H 74.741 CH₃ H 2-furyl H 74.742 CH₃ H 3-furyl H 74.743 CH₃ H 1-methyl-1,2,3-triazol-4-yl H 74.744 CH₃ H 2-methylthiopyrimidin-4-yl H 74.745 CH₃ H 5-methyl-2-methylthiopyrimidin-4-yl H 74.746 CH₃ H pyrazin-2-yl H 74.747 CH₃ H 3,6-dimethylpyrazin-2-yl H 74.748 CH₃ H 3-cyanopyrazin-2-yl H 74.749 CH₃ H quinolin-2-yl H 74.750 CH₃ H 3-ethylquinolin-2-yl H 74.751 CH₃ H benzyl H 74.752 CH₃ H 4-fluorobenzyl H 74.753 CH₃ H 4-chlorobenzyl H 74.754 CH₃ H 4-methylbenzyl H 74.755 CH₃ H 2,4-dimethylbenzyl H 74.756 CH₃ H 2,4,6-trimethylbenzyl H 74.757 CH₃ H H CH₃ 74.758 CH₃ H CH₃ CH₃ 74.759 CH₃ H CH₂CH₃ CH₃ 74.760 CH₃ H n-propyl CH₃ 74.761 CH₃ H isopropyl CH₃ 74.762 CH₃ H n-butyl CH₃ 74.763 CH₃ H isobutyl CH₃ 74.764 CH₃ H sec-butyl CH₃ 74.765 CH₃ H tert-butyl CH₃ 74.766 CH₃ H vinyl CH₃ 74.767 CH₃ H ethynyl CH₃ 74.768 CH₃ H trimethylsilylethynyl CH₃ 74.769 CH₃ H CH₂OH CH₃ 74.770 CH₃ H CH₂OCH₃ CH₃ 74.771 CH₃ H CH₂OCH₂CH₃ CH₃ 74.772 CH₃ H CH₂OCH₂OCH₃ CH₃ 74.773 CH₃ H CH₂OCH₂OCH₂CH₃ CH₃ 74.774 CH₃ H CH₂OCH₂CH₂OCH₃ CH₃ 74.775 CH₃ H CHO CH₃ 74.776 CH₃ H COCH₃ CH₃ 74.777 CH₃ H CO₂H CH₃ 74.778 CH₃ H CO₂CH₃ CH₃ 74.779 CH₃ H CO₂CH₂CH₃ CH₃ 74.780 CH₃ H CONH₂ CH₃ 74.781 CH₃ H CONHCH₃ CH₃ 74.782 CH₃ H CONHCH₂CH₃ CH₃ 74.783 CH₃ H CON(CH₃)₂ CH₃ 74.784 CH₃ H CON(CH₂—CH₃)₂ CH₃ 74.785 CH₃ H CON(CH₃)OCH₃ CH₃ 74.786 CH₃ H CH═NOH CH₃ 74.787 CH₃ H CH═N—OCH₃ CH₃ 74.788 CH₃ H CH═N—OCH₂CH₃ CH₃ 74.789 CH₃ H C(CH₃)═N—OH CH₃ 74.790 CH₃ H C(CH₃)═N—OCH₃ CH₃ 74.791 CH₃ H CH₂OC(O)—NHCH₃ CH₃ 74.792 CH₃ H CH₂NH₂ CH₃ 74.793 CH₃ H CH₂NHCHO CH₃ 74.794 CH₃ H CH₂NHC(O)CH₃ CH₃ 74.795 CH₃ H CH₂NHC(O)OCH₃ CH₃ 74.796 CH₃ H CH(OH)CH₃ CH₃ 74.797 CH₃ H CH(CH₃)OCH₃ CH₃ 74.798 CH₃ H CN CH₃ 74.799 CH₃ H CH₂SCH₃ CH₃ 74.800 CH₃ H CH₂S(O)CH₃ CH₃ 74.801 CH₃ H CH₂SO₂CH₃ CH₃ 74.802 CH₃ H CH₂SCH₂CH₃ CH₃ 74.803 CH₃ H CH₂S(O)CH₂CH₃ CH₃ 74.804 CH₃ H CH₂SO₂CH₂CH₃ CH₃ 74.805 CH₃ H OCH₃ CH₃ 74.806 CH₃ H OCH₂CH₃ CH₃ 74.807 CH₃ H CH(OCH₃)₂ CH₃ 74.808 CH₃ H CH(OCH₂CH₃)₂ CH₃ 74.809 CH₃ H cyclopropyl CH₃ 74.810 CH₃ H cyclobutyl CH₃ 74.811 CH₃ H cyclopentyl CH₃ 74.812 CH₃ H cyclohexyl CH₃ 74.813 CH₃ H F CH₃ 74.814 CH₃ H Cl CH₃ 74.815 CH₃ H Br CH₃ 74.816 CH₃ H I CH₃ 74.817 CH₃ H phenyl CH₃ 74.818 CH₃ H 2-acetylphenyl CH₃ 74.819 CH₃ H 3-acetylphenyl CH₃ 74.820 CH₃ H 4-acetylphenyl CH₃ 74.821 CH₃ H 2-chlorophenyl CH₃ 74.822 CH₃ H 3-chlorophenyl CH₃ 74.823 CH₃ H 4-chlorophenyl CH₃ 74.824 CH₃ H 2-cyanophenyl CH₃ 74.825 CH₃ H 3-cyanophenyl CH₃ 74.826 CH₃ H 4-cyanophenyl CH₃ 74.827 CH₃ H 2-fluorophenyl CH₃ 74.828 CH₃ H 3-fluorophenyl CH₃ 74.829 CH₃ H 4-fluorophenyl CH₃ 74.830 CH₃ H 2-methoxyphenyl CH₃ 74.831 CH₃ H 3-methoxyphenyl CH₃ 74.832 CH₃ H 4-methoxyphenyl CH₃ 74.833 CH₃ H 2-methylphenyl CH₃ 74.834 CH₃ H 3-methylphenyl CH₃ 74.835 CH₃ H 4-methylphenyl CH₃ 74.836 CH₃ H 2-nitrophenyl CH₃ 74.837 CH₃ H 3-nitrophenyl CH₃ 74.838 CH₃ H 4-nitrophenyl CH₃ 74.839 CH₃ H 2-thiomethylphenyl CH₃ 74.840 CH₃ H 3-thiomethylphenyl CH₃ 74.841 CH₃ H 4-thiomethylphenyl CH₃ 74.842 CH₃ H 2-trifluoromethoxyphenyl CH₃ 74.843 CH₃ H 3-trifluoromethoxyphenyl CH₃ 74.844 CH₃ H 4-trifluoromethoxyphenyl CH₃ 74.845 CH₃ H 2-trifluoromethylphenyl CH₃ 74.846 CH₃ H 3-trifluoromethylphenyl CH₃ 74.847 CH₃ H 4-trifluoromethylphenyl CH₃ 74.848 CH₃ H 2,3-dichlorophenyl CH₃ 74.849 CH₃ H 2,4-dichlorophenyl CH₃ 74.850 CH₃ H 2,5-dichlorophenyl CH₃ 74.851 CH₃ H 2,6-dichlorophenyl CH₃ 74.852 CH₃ H 3,4-dichlorophenyl CH₃ 74.853 CH₃ H 3,5-dichlorophenyl CH₃ 74.854 CH₃ H 2,3-difluorophenyl CH₃ 74.855 CH₃ H 2,4-difluorophenyl CH₃ 74.856 CH₃ H 2,5-difluorophenyl CH₃ 74.857 CH₃ H 2,6-difluorophenyl CH₃ 74.858 CH₃ H 3,4-difluorophenyl CH₃ 74.859 CH₃ H 3,5-difluorophenyl CH₃ 74.860 CH₃ H 2,4,6-trifluorophenyl CH₃ 74.861 CH₃ H 2,4-dimethylphenyl CH₃ 74.862 CH₃ H 2,4,6-trimethylphenyl CH₃ 74.863 CH₃ H 3,4,5-trimethoxyphenyl CH₃ 74.864 CH₃ H 2-chloro-3-cyanophenyl CH₃ 74.865 CH₃ H 2-chloro-4-cyanophenyl CH₃ 74.866 CH₃ H 2-chloro-5-cyanophenyl CH₃ 74.867 CH₃ H 2-chloro-6-cyanophenyl CH₃ 74.868 CH₃ H 3-chloro-2-cyanophenyl CH₃ 74.869 CH₃ H 3-chloro-4-cyanophenyl CH₃ 74.870 CH₃ H 3-chloro-5-cyanophenyl CH₃ 74.871 CH₃ H 5-chloro-2-cyanophenyl CH₃ 74.872 CH₃ H 4-chloro-2-cyanophenyl CH₃ 74.873 CH₃ H 4-chloro-3-cyanophenyl CH₃ 74.874 CH₃ H 2-chloro-3-fluorophenyl CH₃ 74.875 CH₃ H 2-chloro-4-fluorophenyl CH₃ 74.876 CH₃ H 2-chloro-5-fluorophenyl CH₃ 74.877 CH₃ H 2-chloro-6-fluorophenyl CH₃ 74.878 CH₃ H 3-chloro-2-fluorophenyl CH₃ 74.879 CH₃ H 3-chloro-4-fluorophenyl CH₃ 74.880 CH₃ H 3-chloro-5-fluorophenyl CH₃ 74.881 CH₃ H 5-chloro-2-fluorophenyl CH₃ 74.882 CH₃ H 4-chloro-2-fluorophenyl CH₃ 74.883 CH₃ H 4-chloro-3-fluorophenyl CH₃ 74.884 CH₃ H 2-chloro-3-methylphenyl CH₃ 74.885 CH₃ H 2-chloro-4-methylphenyl CH₃ 74.886 CH₃ H 2-chloro-5-methylphenyl CH₃ 74.887 CH₃ H 2-chloro-6-methylphenyl CH₃ 74.888 CH₃ H 3-chloro-2-methylphenyl CH₃ 74.889 CH₃ H 3-chloro-4-methylphenyl CH₃ 74.890 CH₃ H 3-chloro-5-methylphenyl CH₃ 74.891 CH₃ H 5-chloro-2-methylphenyl CH₃ 74.892 CH₃ H 4-chloro-2-methylphenyl CH₃ 74.893 CH₃ H 4-chloro-3-methylphenyl CH₃ 74.894 CH₃ H 2-cyano-3-fluorophenyl CH₃ 74.895 CH₃ H 2-cyano-4-fluorophenyl CH₃ 74.896 CH₃ H 2-cyano-5-fluorophenyl CH₃ 74.897 CH₃ H 2-cyano-6-fluorophenyl CH₃ 74.898 CH₃ H 3-cyano-2-fluorophenyl CH₃ 74.899 CH₃ H 3-cyano-4-fluorophenyl CH₃ 74.901 CH₃ H 3-cyano-5-fluorophenyl CH₃ 74.902 CH₃ H 5-cyano-2-fluorophenyl CH₃ 74.903 CH₃ H 4-cyano-2-fluorophenyl CH₃ 74.904 CH₃ H 4-cyano-3-fluorophenyl CH₃ 74.905 CH₃ H 2-fluoro-3-methylphenyl CH₃ 74.906 CH₃ H 2-fluoro-4-methylphenyl CH₃ 74.907 CH₃ H 2-fluoro-5-methylphenyl CH₃ 74.908 CH₃ H 2-fluoro-6-methylphenyl CH₃ 74.909 CH₃ H 3-fluoro-2-methylphenyl CH₃ 74.910 CH₃ H 3-fluoro-4-methylphenyl CH₃ 74.911 CH₃ H 3-fluoro-5-methylphenyl CH₃ 74.912 CH₃ H 5-fluoro-2-methylphenyl CH₃ 74.913 CH₃ H 4-fluoro-2-methylphenyl CH₃ 74.914 CH₃ H 4-fluoro-3-methylphenyl CH₃ 74.915 CH₃ H pyridin-2-yl CH₃ 74.916 CH₃ H pyridin-3-yl CH₃ 74.917 CH₃ H pyridin-4-yl CH₃ 74.918 CH₃ H 3-chloropyridin-2-yl CH₃ 74.919 CH₃ H 4-chloropyridin-2-yl CH₃ 74.920 CH₃ H 5-chloropyridin-2-yl CH₃ 74.921 CH₃ H 6-chloropyridin-2-yl CH₃ 74.922 CH₃ H 2-chloropyridin-3-yl CH₃ 74.923 CH₃ H 4-chloropyridin-3-yl CH₃ 74.924 CH₃ H 5-chloropyridin-3-yl CH₃ 74.925 CH₃ H 2-chloropyridin-4-yl CH₃ 74.926 CH₃ H 3-chloropyridin-4-yl CH₃ 74.927 CH₃ H 2-chloropyridin-5-yl CH₃ 74.928 CH₃ H 3-cyanopyridin-2-yl CH₃ 74.929 CH₃ H 4-cyanopyridin-2-yl CH₃ 74.930 CH₃ H 5-cyanopyridin-2-yl CH₃ 74.931 CH₃ H 6-cyanopyridin-2-yl CH₃ 74.932 CH₃ H 2-cyanopyridin-3-yl CH₃ 74.933 CH₃ H 4-cyanopyridin-3-yl CH₃ 74.934 CH₃ H 5-cyanopyridin-3-yl CH₃ 74.935 CH₃ H 2-cyanopyridin-5-yl CH₃ 74.936 CH₃ H 3-fluoropyridin-2-yl CH₃ 74.937 CH₃ H 4-fluoropyridin-2-yl CH₃ 74.938 CH₃ H 5-fluoropyridin-2-yl CH₃ 74.939 CH₃ H 6-fluoropyridin-2-yl CH₃ 74.940 CH₃ H 2-fluoropyridin-3-yl CH₃ 74.941 CH₃ H 4-fluoropyridin-3-yl CH₃ 74.942 CH₃ H 5-fluoropyridin-3-yl CH₃ 74.943 CH₃ H 2-fluoropyridin-5-yl CH₃ 74.944 CH₃ H 3-nitropyridin-2-yl CH₃ 74.945 CH₃ H 4-nitropyridin-2-yl CH₃ 74.946 CH₃ H 5-nitropyridin-2-yl CH₃ 74.947 CH₃ H 6-nitropyridin-2-yl CH₃ 74.948 CH₃ H 2-nitropyridin-3-yl CH₃ 74.949 CH₃ H 4-nitropyridin-3-yl CH₃ 74.950 CH₃ H 5-nitropyridin-3-yl CH₃ 74.951 CH₃ H 2-nitropyridin-5-yl CH₃ 74.952 CH₃ H 3-trifluoromethylpyridin-2-yl CH₃ 74.953 CH₃ H 4-trifluoromethylpyridin-2-yl CH₃ 74.954 CH₃ H 5-trifluoromethylpyridin-2-yl CH₃ 74.955 CH₃ H 6-trifluoromethylpyridin-2-yl CH₃ 74.956 CH₃ H 2-trifluoromethylpyridin-3-yl CH₃ 74.957 CH₃ H 4-trifluoromethylpyridin-3-yl CH₃ 74.958 CH₃ H 5-trifluoromethylpyridin-3-yl CH₃ 74.959 CH₃ H 2-trifluoromethylpyridin-5-yl CH₃ 74.960 CH₃ H 2,6-bis(trifluoromethyl)pyridin-3-yl CH₃ 74.961 CH₃ H 2,6-bis(trifluoromethyl)pyridin-4-yl CH₃ 74.962 CH₃ H 3,5-bis(trifluoromethyl)pyridin-2-yl CH₃ 74.963 CH₃ H 2-thienyl CH₃ 74.964 CH₃ H 3-thienyl CH₃ 74.965 CH₃ H 5-cyanothien-2-yl CH₃ 74.966 CH₃ H 2-furyl CH₃ 74.967 CH₃ H 3-furyl CH₃ 74.968 CH₃ H 1-methyl-1,2,3-triazol-4-yl CH₃ 74.969 CH₃ H 2-methylthiopyrimidin-4-yl CH₃ 74.970 CH₃ H 5-methyl-2-methylthiopyrimidin-4-yl CH₃ 74.971 CH₃ H pyrazin-2-yl CH₃ 74.972 CH₃ H 3,6-dimethylpyrazin-2-yl CH₃ 74.973 CH₃ H 3-cyanopyrazin-2-yl CH₃ 74.974 CH₃ H quinolin-2-yl CH₃ 74.975 CH₃ H 3-ethylquinolin-2-yl CH₃ 74.976 CH₃ H benzyl CH₃ 74.977 CH₃ H 4-fluorobenzyl CH₃ 74.978 CH₃ H 4-chlorobenzyl CH₃ 74.979 CH₃ H 4-methylbenzyl CH₃ 74.980 CH₃ H 2,4-dimethylbenzyl CH₃ 74.981 CH₃ H 2,4,6-trimethylbenzyl CH₃ 74.982 CH₃ H H CH₂OH 74.983 CH₃ H H CH₂OCH₃ 74.984 CH₃ H H CH₂OCH₂CH₃ 74.985 CH₃ H H CHO 74.986 CH₃ H H COCH₃ 74.987 CH₃ H H CO₂H 74.988 CH₃ H H CO₂CH₃ 74.989 CH₃ H H CO₂CH₂CH₃ 74.990 CH₃ H H CONH₂ 74.991 CH₃ H H CONHCH₃ 74.992 CH₃ H H CONHCH₂CH₃ 74.993 CH₃ H H CON(CH₃)₂ 74.994 CH₃ H H CON—(CH₂CH₃)₂ 74.995 CH₃ H H CON(CH₃)O—CH₃ 74.996 CH₃ H H CH═NOH 74.997 CH₃ H H CH═NOCH₃ 74.998 CH₃ H H CH═NOCH₂—CH₃ 74.999 CH₃ H H C(CH₃)═NOH 74.1000 CH₃ H H C(CH₃)═NO—CH₃ 74.1001 CH₃ H H CH₂OC(O)NH—CH₃ 74.1002 CH₃ H H CH₂NH₂ 74.1003 CH₃ H H CH₂NHCHO 74.1004 CH₃ H H CH₂NHC(O)—CH₃ 74.1005 CH₃ H H CH₂NHC(O)OCH₃ 74.1006 CH₃ H H NHCO₂CH₃ 74.1007 CH₃ H H NHCO₂—C(CH₃)₃ 74.1008 CH₃ H H CH(OH)CH₃ 74.1009 CH₃ H H CH(CH₃)OCH₃ 74.1010 CH₃ H H CN 74.1011 CH₃ H H CH₂SCH₃ 74.1012 CH₃ H H CH₂S(O)CH₃ 74.1013 CH₃ H H CH₂SO₂CH₃ 74.1014 CH₃ H H CH₂SCH₂CH₃ 74.1015 CH₃ H H CH₂S(O)CH₂—CH₃ 74.1016 CH₃ H H CH₂SO₂CH₂—CH₃ 74.1017 CH₃ H H OCH₃ 74.1018 CH₃ H H OCH₂CH₃ 74.1019 CH₃ H H CH(OCH₃)₂ 74.1020 CH₃ H H CH—(OCH₂CH₃)₂ 74.1021 CH₃ H H CH₂CH₃ 74.1022 CH₃ H H CH₂CH₂CH₃ 74.1023 CH₃ H H CH(CH₃)₂ 74.1024 CH₃ H H C(CH₃)₃ 74.1025 CH₃ H H CH₂CH(CH₃)₂ 74.1026 CH₃ H H CH₂C(CH₃)₃ 74.1027 CH₃ H H CH₂CN 74.1028 CH₃ H H cyclopropyl 74.1029 CH₃ H H cyclobutyl 74.1030 CH₃ H H cyclopentyl 74.1031 CH₃ H H cyclohexyl 74.1032 CH₃ H H CH₂-cyclopropyl 74.1033 CH₃ H H benzyl 74.1034 CH₃ H H CH₂CF₃

Table 75 covers compounds of formula (AH), wherein R¹ is ethyl, R² and R⁴ are methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 76 covers compounds of formula (AH), wherein Wand R⁴ are ethyl, R² is methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 77 covers compounds of formula (AH), wherein R¹, R² and R⁴ are ethyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 78 covers compounds of formula (AH), wherein R¹ and R² are methyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 79 covers compounds of formula (AH), wherein R¹ and R² are methyl, R⁴ is methoxy, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 80 covers compounds of formula (AH), wherein R¹ and R² are methyl, R⁴ is chlorine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 81 covers compounds of formula (AH), wherein R¹ and R² are methyl, R⁴ is bromine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 82 covers compounds of formula (AH), wherein R¹ and R² are methyl, R⁴ is iodine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 83 covers compounds of formula (AH), wherein R¹ and R² are methyl, R⁴ is ethynyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 84 covers compounds of formula (AH), wherein R¹ and R² are methyl, R⁴ is vinyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 85 covers compounds of formula (AH), wherein R¹ is ethyl, R² is methyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 86 covers compounds of formula (AH), wherein R¹ is ethyl, R² is methyl, R⁴ is methoxy, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 87 covers compounds of formula (AH), wherein R¹ is ethyl, R² is methyl, R⁴ is chlorine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 88 covers compounds of formula (AH), wherein R¹ is ethyl, R² is methyl, R⁴ is bromine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 89 covers compounds of formula (AH), wherein R¹ is ethyl, R² is methyl, R⁴ is iodine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 90 covers compounds of formula (AH), wherein R¹ is ethyl, R² is methyl, R⁴ is ethynyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 91 covers compounds of formula (AH), wherein R¹ is ethyl, R² is methyl, R⁴ is vinyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 92 covers compounds of formula (AH), wherein R¹ is ethynyl, R² is methyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 93 covers compounds of formula (AH), wherein R¹ is ethynyl, R² is methyl, R⁴ is methoxy, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 94 covers compounds of formula (AH), wherein R¹ is ethynyl, R² is methyl, R⁴ is chlorine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 95 covers compounds of formula (AH), wherein R¹ is ethynyl, R² is methyl, R⁴ is bromine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 96 covers compounds of formula (AH), wherein R¹ is ethynyl, R² is methyl, R⁴ is iodine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 97 covers compounds of formula (AH), wherein R¹ and R⁴ are ethynyl, R² is methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 98 covers compounds of formula (AH), wherein R¹ is vinyl, R² is methyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 99 covers compounds of formula (AH), wherein R¹ is vinyl, R² is methyl, R⁴ is methoxy, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 100 covers compounds of formula (AH), wherein R¹ is vinyl, R² is methyl, R⁴ is chlorine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 101 covers compounds of formula (AH), wherein R¹ is vinyl, R² is methyl, R⁴ is bromine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 102 covers compounds of formula (AH), wherein R¹ is vinyl, R² is methyl, R⁴ is iodine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 103 covers compounds of formula (AH), wherein R¹ and R⁴ are vinyl, R² is methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 104 covers compounds of formula (AH), wherein R¹ is methyl, R², R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 105 covers compounds of formula (AH), wherein R¹ is methyl, R² is methoxy, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 106 covers compounds of formula (AH), wherein R¹ is methyl, R² is trifluoromethyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 107 covers compounds of formula (AH), wherein R¹ is methyl, R² is ethyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 108 covers compounds of formula (AH), wherein R¹ is methyl, R² is ethynyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 109 covers compounds of formula (AH), wherein R¹ is methyl, R² is vinyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 110 covers compounds of formula (AH), wherein R¹ is methyl, R² is chlorine, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 111 covers compounds of formula (AH), wherein R¹ is methyl, R² is bromine, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 112 covers compounds of formula (AH), wherein R¹ is methyl, R² is iodine, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 113 covers compounds of formula (AH), wherein R¹ is ethyl, R², R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 114 covers compounds of formula (AH), wherein R¹ is ethyl, R² is methoxy, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 115 covers compounds of formula (AH), wherein R¹ and R² are ethyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 116 covers compounds of formula (AH), wherein R¹ is ethyl, R² is trifluoromethyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 117 covers compounds of formula (AH), wherein R¹ is ethyl, R² is ethynyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 118 covers compounds of formula (AH), wherein R¹ is ethyl, R² is vinyl, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 119 covers compounds of formula (AH), wherein R¹ is ethyl, R² is chlorine, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 120 covers compounds of formula (AH), wherein R¹ is ethyl, R² is bromine, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 121 covers compounds of formula (AH), wherein R¹ is ethyl, R² is iodine, R³, R⁴, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 122 covers compounds of formula (AH), wherein R¹ and R⁴ are methyl, R² is chlorine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 123 covers compounds of formula (AH), wherein R¹ and R⁴ are methyl, R² is bromine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 124 covers compounds of formula (AH), wherein R¹ and R⁴ are methyl, R² is iodine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 125 covers compounds of formula (AH), wherein R¹ is methyl, R² is chlorine, R³ is hydrogen, R⁴ is ethyl, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 126 covers compounds of formula (AH), wherein R¹ is methyl, R² is bromine, R³ is hydrogen, R⁴ is ethyl, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 127 covers compounds of formula (AH), wherein R¹ is methyl, R² is iodine, R³ is hydrogen, R⁴ is ethyl, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 128 covers compounds of formula (AH), wherein R¹ and R⁴ are ethyl, R² is chlorine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 129 covers compounds of formula (AH), wherein R¹ and R⁴ are methyl, R² is bromine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 130 covers compounds of formula (AH), wherein R¹ and R⁴ are ethyl, R² is iodine, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 131 covers compounds of formula (AH), wherein R¹ is methyl, R² is chlorine, R³ is hydrogen, R⁴ is methoxy, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 132 covers compounds of formula (AH), wherein R¹ is methyl, R² is bromine, R³ is hydrogen, R⁴ is methoxy, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 133 covers compounds of formula (AH), wherein R¹ is ethyl, R² is chlorine, R³ is hydrogen, R⁴ is methoxy, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 134 covers compounds of formula (AH), wherein R¹ is ethyl, R² is bromine, R³ is hydrogen, R⁴ is methoxy, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 135 covers compounds of formula (AH), wherein R¹ and R⁴ are methyl, R² is methoxy, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 136 covers compounds of formula (AH), wherein R¹ is methyl, R² is methoxy, R³ is hydrogen, R⁴ is ethyl, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 137 covers compounds of formula (AH), wherein R¹ and R⁴ are ethyl, R² is methoxy, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 138 covers compounds of formula (AH) wherein R¹, R², R³ and R⁴ are methyl, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 139 covers compounds of formula (A), wherein R¹ is difluoromethoxy, R² and R⁴ are methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 140 covers compounds of formula (A), wherein R¹ is difluoromethoxy, R² is methyl, R⁴ is ethyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 141 covers compounds of formula (A), wherein R¹ is trifluoromethoxy, R² and R⁴ are methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 142 covers compounds of formula (A), wherein R¹ is trifluoromethoxy, R² is methyl, R⁴ is ethyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 143 covers compounds of formula (A), wherein R¹ is cyclopropyl, R² and R⁴ are methyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 144 covers compounds of formula (A), wherein R¹ is cyclopropyl, R² is methyl, R⁴ is ethyl, R³, R⁵ and R¹² are hydrogen and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 145 covers compounds of formula (A), wherein R¹ and R² are methyl, R³, R⁵ and R¹² are hydrogen, R⁴ is cyclopropyl and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Table 146 covers compounds of formula (A), wherein R¹ and R² are ethyl, R³, R⁵ and R¹² are hydrogen, R⁴ is cyclopropyl and R⁶, R⁸, R⁹, and R¹¹ are as defined in Table 74.

Example 25 Preparation of (1RS,2SR,6RS,7SR)-5-oxo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-3-en-3-yl 2,2-dimethylpropionate

A solution of pivaloyl chloride (0.055 g, 0.57 mmol) in dichloromethane (2 ml) is added dropwise to a solution of (1RS,2SR,6RS,7SR)-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione (0.12 g, 0.42 mmol) in dichloromethane (2 ml) at room temperature and the reaction mixture is stirred for 2 minutes. A solution of triethylamine (0.08 ml) in dichloromethane (1 ml) is added and the reaction mixture is stirred at room temperature for 3 hours. The reaction mixture is diluted with dichloromethane (20 ml) and washed with saturated aqueous sodium bicarbonate solution. The organic phase is dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated under reduced pressure to give (1RS,2SR,6RS,7SR)-5-oxo-4-(2,4,6-trimethylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]dec-3-en-3-yl 2,2-dimethylpropionate as a colourless oil.

¹H NMR (400 MHz, CDCl₃) δ_(H) 6.84 (1H, s), 6.82 (1H, s), 4.75 (1H, d), 4.55 (1H, d), 3.45 (1H, d), 2.78 (1H, d), 2.24 (3H, s), 2.09 (3H, s), 2.02 (3H, s), 1.89-1.83 (2H, m), 1.63-1.59 (2H, m), 1.11 (9H, s).

Example 26 Preparation of carbonic acid (1RS,2SR,6RS,7SR)-5-oxo-4-(2,6-diethyl-4-methylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]-dec-3-en-3-yl ester ethyl ester

A solution of ethyl chloroformate (0.071 g, 0.65 mmol) in dichloromethane (0.5 ml) is added dropwise to a solution of (1RS,2SR,6RS,7SR)-4-(2,6-diethyl-4-methylphenyl)-10-oxatricyclo[5.2.1.0^(2,6)]decane-3,5-dione (0.172 g, 0.55 mmol) in dichloromethane (2 ml) at 0° C. and the reaction mixture is stirred. A solution of triethylamine (0.066 g, 0.65 mmol) in dichloromethane (1 ml) is added and the reaction mixture is stirred at room temperature for 17 hours, warming slowly to room temperature. The reaction mixture is diluted with dichloromethane (3 ml) and washed with saturated aqueous sodium bicarbonate solution. The organic phase is separated, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated under reduced pressure. The residue is purified by column chromatography on silica gel to give carbonic acid (1RS, 2SR,6RS,7SR)-5-oxo-4-(2,6-diethyl-4-methylphenyl)-10-oxatricyclo-[5.2.1.0^(2,6)]-dec-3-en-3-yl ester ethyl ester as a colourless solid.

¹H NMR (400 MHz, CDCl₃) δ_(H) 1.06 (6H, m), 1.28 (3H, t), 1.63 (2H, m), 1.87 (2H, m), 2.3 (3H, s), 2.35 (4H, m), 2.8 (1H, d), 3.63 (1H, d), 4.22 (2H, q), 4.64 (1H, d), 4.77 (1H, d), 6.91 (2H, d).

Additional compounds in Table P1 below were prepared by similar methods using appropriate starting materials.

TABLE P1 Compound ¹H nmr (CDCl₃ unless stated) or other physical Number Structure data P1

δ_(H) 6.90 (2H, s), 6.45 (1H, dd), 6.35 (1H, dd), 5.30 (1H, d), 5.25 (1H, d), 3.65 (3H, s), 3.65 (1H, dd), 3.45 (1H, dd), 2.35 (4H, m), 2.30 (3H, s), 1.10 (6H, m). P2

δ_(H) 6.90 (2H, m), 4.85 (2H, m), 3.70 (3H, s), 3.60 (1H, m), 3.35 (1H, dd), 2.50 (2H, m), 2.35 (2H, m), 2.30 (3H, s), 1.90-1.75 (4H, m), 1.20 (3H, t), 1.10 (3H, t) P3

δ_(H) 6.87 (1H, s), 6.85 (1H, s), 4.74 (1H, d), 4.68 (2H, t), 4.65 (1H, d), 3.53 (1H, d), 2.79 (1H, d), 2.56 (1H, t), 2.26 (3H, s), 2.09 (3H, s), 2.05 (3H, s), 1.94-1.80 (2H, m), 1.67-1.56 (2H, m). P4

δ_(H) 6.87 (1H, s), 6.85 (1H. s), 4.85-4.78 (1H, m), 4.74 (1H, d), 4.64 (1H, d), 3.51 (1H, d), 2.77 (1H, d), 2.25 (3H, s), 2.09 (3H, s), 2.06 (3H, s), 1.93- 1.79 (2H, m), 1.67-1.54 (2H, m), 1.25 (3H, d), 1.20 (3H, d). P5

δ_(H) 6.88 (1H, s), 6.86 (1H, s), 4.73 (1H, d), 4.59 (1H, d), 3.56 (1H, d), 2.76 (1H, d), 2.27 (3H, s), 2.10 (3H, s), 2.04 (3H, s), 1.89-1.80 (2H, m), 1.69-1.56 (3H, m), 1.01-0.92 (4H, m). P6

δ_(H) 6.86 (1H, s), 6.84 (1H, s), 4.74 (1H, d), 4.58 (1H, d), 3.48 (1H, d), 2.77 (1H, d), 2.40-2.35 (2H, m), 2.26 (3H, s), 2.09 (3H, s), 2.04 (3H, s), 1.93- 1.82 (2H, m), 1.65-1.48 (4H, m), 1.31-1.17 (6H, m), 0.86 (3H, t). P7

δ_(H) 7.38-7.37 (3H, m), 7.19-7.18 (2H, m), 6.97 (2H, s), 6.68 (1H, dd), 6.55 (1H, d), 5.08 (1H, s with fine splitting), 4.82-4.81 (2H, m), 4.13-4.10 (1H, m), 4.03-4.00 (1H, m), 3.13 (1H, dd), 2.89 (1H, dd), 2.54-2.45 (4H, m), 2.37 (3H, s), 1.20- 1.16 (6H, m). P8

δ_(H) 7.35-7.32 (3H, m), 7.15-7.13 (2H, m), 6.93 (1H, s), 6.92 (1H, s), 6.54-6.49 (2H, m), 5.14 (1H, d), 4.71-4.64 (2H, m), 4.15-4.08 (2H, m), 2.99 (1H, d), 2.84 (1H, d), 2.59-2.39 (4H, m), 2.32 (3H, s), 1.17-1.13 (6H, m). P9

δ_(H) 6.84 (1H, s), 6.82 (1H, s), 4.73 (1H, d), 4.57- 4.55 (1H, m), 3.46-3.44 (1H, m), 2.77 (1H, d), 2.46-2.35 (1H, m), 2.23 (3H, s), 2.08 (3H, s), 2.02 (3H, s), 1.92-1.80 (2H, m), 1.04 (3H, d), 0.93 (3H, t). P10

δ_(H) 6.86 (1H, s), 6.84 (1H, s), 4.74 (1H, d), 4.56 (1H, d), 3.49 (1H, d), 2.78 (1H, d), 2.65-2.58 (1H, m), 2.25 (3H, s), 2.09 (3H, s), 2.03 (3H, s), 1.93- 1.79 (2H, m), 1.66-1.56 (2H, m), 1.13 (3H, d), 1.06 (3H, d). P11

δ_(H) 7.34-7.31 (3H, m), 7.15-7.12 (2H, m), 6.90 (2H, s), 6.50 (2H, s), 5.05 (1H, s), 4.79-4.72 (4H, m), 4.23 (1H, d), 3.97 (1H, d), 3.65-3.58 (2H, m), 3.06 (1H, d), 2.66 (1H, d), 2.54-2.34 (4H, m), 2.31 (3H, s), 1.20 (3H, t), 1.15-1.10 (6H, m). P12

δ_(H) 7.33-7.30 (3H, m), 7.14-7.12 (2H, m), 6.90 (2H, s), 6.51 (1H, dd), 6.45 (1H, d), 5.11 (1H, d), 5.05 (1H, d), 4.81-4.76 (1H, m), 4.73-4.72 (2H, m), 4.30 (1H, d), 3.17-3.12 (2H, m), 3.06 (1H, d), 2.69 (1H, d), 2.52-2.35 (4H, m), 2.31 (3H, s), 1.53-1.47 (2H, m), 1.15-1.11 (6H, m), 0.90 (3H, t). P13

δ_(H) 7.33-7.30 (3H, m), 7.15-7.11 (2H, m), 6.86 (2H, s), 6.50-6.49 (2H, m), 5.11 (0.5H, s), 5.04 (0.5H, s), 4.76-4.66 (2H, m), 4.16-4.11 (1H, m), 3.77-3.74 (1H, m), 3.43 (1.5H, s), 3.34 (1.5H, s), 3.03 (0.5H, s), 2.94 (0.5H, s), 2.77 (0.5H, d), 2.62 (0.5H, d), 2.27 (1.5H, s), 2.19 (1.5H, s), 2.12 (1.5H, s), 2.08 (1.5H, s), 2.07 (3H, s). P14

δ_(H) 1.04 (6H, m), 1.08 (9H, s), 1.6 (2H, m), 1.85 (2H, m), 2.3 (3H, s), 2.33 (4H, m), 2.79 (1H, d), 3.58 (1H, d), 4.54 (1H, d), 4.74 (1H, d), 6.85 (1H, s) 6.88 (1H, s). P15

δ_(H) 1.04 (6H, m), 1.6 (2H, m), 1.85 (2H, m), 2.3 (3H, s), 2.35 (4H, m), 2.8 (1H, d), 3.63 (1H, d), 4.66 (1H, d), 4.7 (1H, s), 4.75 (1H, d), 6.9 (2H, s). P16

δ_(H) 1.04 (6H, m), 1.2 (3H, m), 1.35 (1H, m), 1.6 (8H, m), 1.85 (2H, m), 2.32 (9H, m), 2.8 (1H, d), 3.58 (1H, d), 3.67 (3H, s), 4.58 (1H, d), 4.75 (1H, d), 6.9 (2H, s). P17

δ_(H) 1.04 (6H, m), 1.3-1.8 (14H, m), 2.3 (3H, s), 2.34 (5H, m), 2.79 (1H, d), 3.6 (1H, d), 4.54 (1H, d), 4.75 (1H, d), 6.89 (2H, d). P18

δ_(H) 1.06 (6H, m), 1.28 (3H, t), 1.63 (2H, m), 1.87 (2H, m), 2.3 (3H, s), 2.35 (4H, m), 2.8 (1H, d), 3.63 (1H, d), 4.22 (2H, q), 4.64 (1H, d), 4.77 (1H, d), 6.91 (2H, d). P19

δ_(H) 0.85 (6H, d), 1.05 (6H, m), 1.61 (2H, m), 1.85 (2H, m), 1.98 (1H, m), 2.28 (2H, d), 2.3 (3H, s), 2.35 (4H, m), 2.8 (1H, d), 3.58 (1H, d), 4.58 (1H, d), 4.75 (1H, d), 6.89 (2H, d). P20

δ_(H) 0.84 (3H, t), 1.05 (6H, m), 1.23 (8H, m), 1.62 (2H, m), 1.86 (2H, m), 2.3 (3H, s), 2.37 (6H, m), 2.8 (1H, d), 3.59 (1H, d), 4.58 (1H, d), 4.75 (1H, d), 6.9 (2H, d). P21

δ_(H) 0.95 (4H, m), 1.05 (6H, m), 1.63 (3H, m), 1.85 (2H, m), 2.3 (3H, s), 2.35 (4H, m), 2.77 (1H, d), 3.65 (1H, d), 4.59 (1H, d), 4.74 (1H, d), 6.9 (2H, d) P22

δ_(H) 1.07 (9H, m), 1.6 (2H, m), 1.85 (2H, m), 2.31 (3H, s), 2.39 (6H, m), 2.79 (1H, d), 3.62 (1H, d), 4.58 (1H, d), 4.74 (1H, d), 6.9 (2H, d). P23

δ_(H) 1.06 (6H, m), 1.62 (2H, m), 1.87 (2H, m), 2.3 (3H, s), 2.35 (4H, m), 2.8 (1H, d), 3.52 (1H, d), 4.62 (3H, m), 4.75 (1H, d), 5.31 (2H, m), 5.85 (1H, m), 6.91 (2H, d). P24

δ_(H) 0.9 (6H, d), 1.07 (6H, m), 1.61 (2H, m), 1.86 (2H, m), 1.92 (1H, m), 2.31 (3H, s), 2.32 (4H, m), 2.8 (1H, d), 3.52 (1H, d), 3.94 (2H, m), 4.64 (1H, d), 4.76 (1H, d), 6.91 (2H, d). P25

δ_(H) 1.07 (6H, m), 1.62 (2H, m), 1.87 (2H, m), 2.31 (3H, s), 2.36 (4H, m), 2.56 (1H, m), 2.81 (1H, d), 3.63 (1H, d), 4.67 (1H, d), 4.75 (2H, m), 6.9 (2H, d). P26

δ_(H) 1.05 (9H, m), 1.13 (3H, d), 1.61 (2H, m), 1.87 (2H, m), 2.31 (3H, s), 2.36 (4H, m), 2.6 (1H, m), 2.79 (1H, d) 3.61 (1H, d), 4.57 (1H, d), 4.76 (1H, d), 6.89 (2H, d). P27

Approximately 1:1 ratio of Isomer A:Isomer B δ_(H) 6.87-6.86 (2H, m), 4.84-4.77 (1H, m), 4.60 (1H, d), 3.89 (1H, d), 3.70 (1H, d), 3.60 (1H, d), 3.41 (3H, s), 2.80 (1H, d), 2.25 (3H, s), 2.10 (3H, s), 2.05 (3H, s), 2.03-1.96 (2H, m), 1.72-1.65 (2H, m), 1.25 (3H, d), 1.19 (3H, d).

P28

Approximately 1:1 ratio of Isomer A:Isomer B δ_(H) 6.88-6.86 (2H, m), 4.74-4.60 (3H, m), 3.89- 6.63 (3H, m), 3.41 (3H, s), 2.92 (0.5H, d), 2.83- 2.81 (0.5H, m), 2.56-2.55 (1H, m), 2.26 (3H, s), 2.10 (1.5H, 5), 2.09 (1.5H, s), 2.04 (1.5H, s), 2.03 (1.5H, s), 2.00-1.65 (4H, m).

P29

Approximately 1:1 ratio of Isomer A:Isomer B δ_(H) 6.86-6.84 (2H, m), 4.55 (1H, d), 3.89 (1H, d), 3.70 (1H, d), 3.59 (1H, d), 3.41 (3H, s), 2.81 (1H, d), 2.39-2.33 (2H, m), 2.25 (3H, s), 2.09 (3H, s), 2.03 (3H, s), 2.00-1.95 (1H, m), 1.66-1.49 (3H, m), 1.38-1.13 (8H, m), 0.90-0.84 (3H, m).

P30

Approximately 1:1 ratio of Isomer A:Isomer B δ_(H) 6.88-6.86 (2H, m), 4.55 (1H, d), 3.89 (1H, d), 3.71-3.65 (2H, m), 3.41 (3H, s), 2.79 (1H, d), 2.27 (3H, s), 2.11 (3H, s), 2.03 (3H, s), 1.78-1.50 (4H, m), 1.07-1.04 (1H, m), 0.99-0.91 (4H, m).

P31

Approximately 1:1 ratio of Isomer A:Isomer B δ_(H) 6.84-6.82 (2H, m), 4.54-4.52 (1H, m), 3.89 (1H, d), 3.70 (1H, d), 3.56 (1H, t), 3.40 (3H, s), 2.80 (1H, d), 2.44-2.37 (1H, m), 2.24 (3H, s), 2.09 (3H, s), 2.02 (3H, s), 1.71-1.35 (6H, m), 1.17-1.02 (3H, m), 0.95-0.67 (3H, m).

P32

Approximately 1:1 ratio of Isomer A:Isomer B δ_(H) 6.85-6.83 (2H, m), 4.52 (1H, d), 3.89 (1H, d), 3.70 (1H, d), 3.58 (1H, d), 3.40 (3H, s), 2.80 (1H, d), 2.62-2.57 (1H, m), 2.24 (3H, s), 2.09 (3H, s), 2.02 (3H, s), 1.71-1.52 (4H, m), 1.11 (3H, t), 1.04 (3H, d).

P33

δ_(H) 6.84 (1H, s), 6.82 (1H, s), 4.75 (1H, d), 4.55 (1H, d), 3.45 (1H, d), 2.78 (1H, d), 2.24 (3H, s), 2.09 (3H, s), 2.02 (3H, s), 1.89-1.83 (2H, m), 1.63- 1.59 (2H, m), 1.11 (9H, s). P34

δ_(H) 6.90 (1H, s), 6.89 (1H, s), 4.73 (1H, d), 4.66 (1H, d), 3.58 (3H, s), 2.91 (1H, d), 2.66 (1H, d), 2.49-2.39 (4H, m), 2.30 (3H, s), 1.88-1.81 (2H, m), 1.62-1.56 (2H, m), 1.12-1.08 (3H, m). P35

δ_(H) 6.93 (2H, br. s), 3.71-3.69 (1H, m), 2.81-2.80 (1H, m), 2.33 (3H, s), 2.20 (3H, s), 2.08 (3H, s), 1.87-1.72 (5H, m), 1.64-1.60 (6H, m), 1.05- 0.99 (4H, m). P36

δ_(H) 6.88 (1H, s), 6.86 (1H, s), 4.71 (1H, dd), 4.61 (1h, dd), 3.65 (1H, d), 2.77 (1H, d), 2.55 (1H, t), 2.26 (3H, s), 2.12 (3H, s), 2.04 (3H, s), 1.82-1.71 (4H, m), 1.56 (3H, s), 1.53 (3H, s). P37

Approximately 1:1 ratio of Isomer A:Isomer B δ_(H) 6.87 (1H, s), 6.85 (1H, s), 4.70 (0.5H, d), 4.55 (0.5H, d), 4.43 (1H, s), 4.26 (1H, s), 3.53 (1H, app t), 2.74 (1H, app t), 2.26 (3H, s), 2.09 (3H, s), 2.04 (3H, s), 1.82-1.63 (3H, m), 1.49-1.41 (2H, m), 1.30-1.26 (1H, m), 0.98-0.90 (7H, m).

P38

Approximately 1:1 ratio of Isomer A:Isomer B δ_(H) 6.87 (1H, s), 6.86 (1H, s), 4.72-4.60 (3H, m), 4.45 (0.5H, s), 4.33 (0.5H, d), 3.77 (1H, s), 3.50 (1H, d), 2.79-2.76 (0.5H, m), 2.56-2.54 (0.5H, m), 2.26 (3H, s), 2.08 (3H, s), 2.05 (3H, s), 1.84- 1.75 (2H, m), 1.52-1.42 (2H, m), 1.30-1.24 (1H, m), 0.96-0.83 (3H, m).

P39

δ_(H) 7.01 (1H, br. s), 6.76 (1H, d), 6.72 (1H, dd), 4.72 (1H, d), 4.65 (1H, d), 3.78 (3H, s), 3.65 (3H, s), 2.88 (1H, d), 2.64 (1H, d), 2.15 (3H, s), 1.80- 1.89 (2H, m), 1.56-1.62 (2H, m). P40

δ_(H) 6.91 (1H, br. s), 6.76 (1H, s), 6.70 (1H, d), 4.73 (1H, d), 4.53 (1H, d), 3.78 (3H, s), 3.43 (1H, s), 2.75 (1H, d), 2.15 (3H, s), 1.93-1.79 (2H, m), 1.65-1.58 (2H, m), 1.16 (9H, s). P41

δ_(H) 7.11-7.05 (1H, m), 7.03-6.99 (1H, m), 6.89 (1H, br. s), 4.73 (1H, d), 4.65 (1H, d), 3.64 (1H, s), 2.89 (1H, d), 2.64 (1H, d), 2.28 (3H, s), 2.13 (3H, s), 1.92-1.78 (2H, m), 1.63-1.57 (2H, m). P42

δ_(H) 7.19 (1H, dd), 6.96 (1H, td), 6.91-6.86 (1H, m), 4.77 (1H, d), 4.70 (1H, d), 3.72 (3H, s), 2.96 (1H, d), 2.70 (1H, d), 2.18 (3H, s), 1.97-1.82 (2H, m), 1.68-1.62 (2H, m). P43

δ_(H) 7.16-7.10 (1H, m), 7.08-7.03 (1H, m), 6.94 (1H, br. s), 4.77 (1H, d), 4.70 (11-1, d), 3.68 (3H, s), 2.93 (1H, d), 2.72-2.66 (1H, m), 2.17 (3H, s), 1.97-1.80 (2H, m), 1.62-1.58 (2H, m). P44

δ_(H) 7.09 (1H, d), 7.04-6.99 (1H, m), 6.76 (1H, br. s), 4.75 (1H, d), 4.54 (1H, d), 3.49-3.41 (1H, m), 2.76 (1H, d), 2.26 (3H, s), 2.17 (3H, s), 1.94-1.79 (2H, m), 1.67-1.59 (2H, m), 1.15 (9H, s). P45

δ_(H) 7.16 (1H, dd), 6.92 (1H, td), 6.74 (1H, br. s), 4.75 (1H, d), 4.54 (1H, d), 3.46 (1H, d), 2.77 (1H, d), 2.17 (3H, s), 1.93-1.82 (2H, m), 1.67-1.57 (2H, m), 1.17 (9H, s). P46

δ_(H) 7.21-7.17 (1H, m), 7.16-7.12 (1H, m), 6.96 (1H, br. s), 4.74 (1H, d), 4.54 (1H, s), 3.45 (1H, d), 2.77 (1H, d), 2.17 (3H, s), 1.94-1.80 (2H, m), 1.67-1.58 (2H, m), 1.17 (9H, s). P47

δ_(H) 6.58 (2H, d), 4.74 (1H, d), 4.55 (1H, d), 3.76 (3H, s), 3.43 (1H, d), 2.82-2.73 (1H, m), 2.11 (3H, s), 2.04 (3H, s), 1.93-1.78 (2H, m), 1.66-1.57 (2H, m), 1.11 (9H, s). P48

δ_(H) 7.33 (1H, d), 7.29 (1H, br. s), 7.23 (1H, dd), 4.75 (1H, d), 4.67 (1H, d), 3.76 (3H, s), 2.94 (1H, s), 2.69 (1H, s), 1.93-1.79 (2H, m), 1.65-1.54 (2H, m). P49

δH 6.60 (2H, d), 4.72 (1H, d), 4.65 (1H, d), 3.76 (3H, s), 3.58 (3H, s), 2.88 (1H, d), 2.64 (1H, d), 2.13 (3H, s), 2.10 (3H, s), 1.90-1.77 (2H, m), 1.64- 1.54 (2H, m). P50

δ_(H) 7.14 (2H, d), 5.34 (1H, s), 5.04 (1H, s), 4.73 (1H, d), 4.66 (1H, d), 3.58 (3H, s), 2.90 (1H, d), 2.66 (1H, d), 2.17 (3H, s), 2.14 (3H, s), 2.11 (3H, s), 1.92-1.75 (2H, m), 1.66-1.54 (2H, m). P51

Approximately 1:1 mixture of Isomer A:Isomer B Isomer A: δ_(H) 7.81 (2H, s), 6.87 (1H, s), 6.83 (1H, s), 4.83 (1H, d), 4.69 (1H, s), 3.64 (1H, d), 3.22 (1H, dd), 2.99 (1H, d), 2.38 (1H, dd), 2.25 (3H, s), 2.11 (3H, s), 2.04 (3H, s), 1.99-1.96 (1H, m), 1.23 (3H, s), 1.13 (6H, s). Isomer B: δ_(H) 7.84 (2H, s), 6.87 (1H, s), 6.84 (1H, s), 4.99 (1H, d), 4.50 (1H, s), 3.64 (1H, d), 3.24 (1H, dd), 2.94 (1H, d), 2.35 (1H, dd), 2.25 (3H, s), 2.10 (3H, s), 2.04 (3H, s), 1.91-1.89 (1H, m), 1.07 (9H s).

P52

Approximately 1:1:1:1 mixture of Isomer A:Isomer B:Isomer C:Isomer D δ_(H) 6.84 (1H, s), 6.82 (1H, s), 4.71 (0.25H, d), 4.68 (0.25H, d), 4.60 (0.25H, d), 4.52 (0.25H, d), 4.48 (0.25H, d), 4.45 (0.25H, s), 4.41 (0.25H, d), 4.23 (0.25H, s), 3.79 (0.25H, d), 3.43 (0.514, t), 3.04 (0.25H, d), 2.77-2.73 (0.75H, m), 2.24 (3H, s), 2.19-2.11 (1H, m), 2.09 (3H, s), 2.03 (3H, s), 1.84-1.73 (1H, m), 1.52-1.39 (2H, m), 1.28- 1.26 (1H, m), 1.12-1.10 (9H, m), 1.00-0.90 (3H, m).

Biological Examples Test Example 1

Monocotyledonous and dicotyledonous test plants were sown in standard soil in pots. After cultivation for one day (pre-emergence) or after 10 days cultivation (post-emergence) under controlled conditions in a glasshouse, the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in 0.6 ml acetone and 45 ml formulation solution containing 10.6% Emulsogen EL (Registry number 61791-12-6), 42.2% N-methylpyrrolidone, 42.2% dipropylene glycol monomethyl ether (Registry number 34590-94-8) and 0.2% X-77 (Registry number 11097-66-8). The test plants were then grown in a greenhouse under optimum conditions until, 15 days later for post-emergence and 20 days for pre-emergence, the test was evaluated (100=total damage to plant; 0=no damage to plant).

Test Plants:

Alopecurus myosuroides (ALOMY), Avena fatua (AVEFA), Lolium perenne (LOLPE), Setaria faberi (SETFA), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG)

Pre-Emergence Activity

Compound Rate Number g/ha ALOMY AVEFA LOLPE SETFA DIGSA ECHCG T1 250 100 100 100 100 100 100 T2 250 100 100 100 90 100 100 T3 250 90 80 100 70 80 100 T4 250 90 90 100 90 100 100 T5 250 100 80 100 80 100 100 T6 250 80 30 100 80 90 90 T7 250 100 80 100 90 80 90 T8 250 100 90 100 100 100 100 T9 250 70 40 100 100 100 100 T10 250 80 70 100 80 80 90 T11 250 30 40 60 20 0 30 T12 250 10 10 40 40 40 0 T13 250 80 80 90 100 100 100 T14 250 90 90 100 100 70 90 T15 250 40 20 40 60 30 80 T16 250 0 10 0 10 0 0 T17 250 100 90 100 100 100 100 T18 250 100 100 100 100 100 100 T19 250 100 90 100 100 90 100 T21 250 90 30 80 70 10 80 T27 250 70 70 70 100 90 100 T34 250 70 30 60 80 60 40 T37 250 60 30 30 0 20 30 T39 250 10 20 30 40 30 30 T40 250 50 60 60 40 60 40 T41 250 50 30 20 60 30 70 T42 250 0 10 0 0 0 30 T43 250 10 20 0 50 20 0 T44 250 80 40 70 80 80 70 T46 250 10 0 30 30 20 70 T47 250 100 80 100 80 70 100 T48 250 100 80 100 100 100 100 T49 250 80 70 100 20 10 80 T52 250 40 30 100 90 90 100 T53 250 10 20 10 10 10 0 T56 250 100 60 100 70 70 100 T57 250 50 30 100 80 60 70 T58 250 0 10 0 0 0 60 T59 250 10 20 30 40 50 30 T60 250 0 40 10 10 30 30 T62 250 70 70 60 80 80 80 T64 250 0 0 10 20 10 50 T65 250 100 90 100 90 100 100 T66 250 30 60 40 100 90 70 T70 250 80 50 100 90 90 100 T71 250 30 0 0 20 50 50 T85 250 40 60 70 70 60 70 T89 250 20 60 40 30 30 20 T90 250 10 60 20 40 60 70 T91 250 20 50 20 50 70 50 T92 250 20 60 30 70 70 90 T93 250 40 30 20 30 30 0 T97 250 100 90 100 90 100 100 T98 250 30 20 20 70 0 30 T99 250 80 60 100 80 80 100 T106 250 90 90 100 100 100 100 T107 250 90 90 100 100 100 100 T125 250 70 70 100 100 100 100 T128 250 70 70 90 100 100 100 T129 250 100 90 90 100 90 100 T134 250 60 20 70 0 50 20 T143 250 50 20 70 70 80 10 T146 250 70 60 90 80 80 80 T147 250 40 0 40 60 40 90 T148 250 60 50 70 60 70 80 T149 250 90 60 80 80 70 90 T150 250 0 0 30 0 0 40 T151 250 50 20 60 20 80 40 T153 250 70 70 80 70 60 70 T154 250 70 50 80 70 70 100 T155 250 60 50 80 60 70 60 T156 250 70 60 70 70 70 70 T157 250 30 — 70 0 0 50 T158 250 60 50 70 70 70 50 T159 250 50 60 40 70 70 70 T160 250 30 50 40 70 40 40 T162 250 70 70 90 10 40 80 T163 250 70 60 90 90 90 80 T165 250 70 20 80 70 50 80 T167 250 30 40 40 0 30 50 T169 250 20 30 40 0 0 0 T170 250 80 40 90 70 70 80 T171 250 30 0 10 70 40 70 T173 250 90 70 100 60 70 70 T174 250 30 30 30 0 40 0 T177 250 60 50 70 50 10 70 T178 250 70 40 80 100 80 100 T179 250 70 60 80 10 60 70 T180 250 30 20 70 40 80 60 T181 250 40 40 80 70 90 100 T182 250 30 50 40 50 80 90 T184 250 30 60 70 90 70 60 T185 250 80 80 100 80 80 80 T187 250 10 20 60 40 20 10 T188 250 40 0 50 70 100 60 T193 250 20 30 60 40 20 20 T194 250 0 20 20 50 70 50 T199 250 0 50 60 60 100 80 T200 250 0 0 70 70 70 90 T203 250 20 20 60 70 70 90 T208 250 50 70 80 80 70 80 P3 250 100 100 100 90 90 100 P4 250 100 100 100 70 90 90 P5 250 100 100 100 90 100 90 P6 250 100 100 100 80 100 90 P9 250 100 100 100 80 90 80 P10 250 100 100 100 80 100 100 P14 250 100 100 100 100 100 100 P15 250 80 90 90 100 100 100 P16 250 100 90 90 100 100 100 P17 250 90 90 100 100 100 100 P18 250 100 100 100 100 100 100 P19 250 100 100 100 100 100 100 P20 250 100 80 100 100 100 100 P21 250 100 100 100 100 100 100 P22 250 100 100 100 100 100 100 P23 250 80 90 100 100 100 100 P24 250 90 90 100 100 100 100 P25 250 100 100 100 100 100 100 P26 250 100 90 100 100 100 100 P27 250 90 80 90 80 90 100 P28 250 90 80 100 80 90 80 P30 250 80 80 90 80 80 90 P33 250 90 70 100 80 80 — P36 250 70 80 100 80 80 100 P37 250 90 90 100 100 100 100

Post-Emergence Activity

Compound Rate Number g/ha ALOMY AVEFA LOLPE SETFA DIGSA ECHCG T1 125 90 90 80 100 100 100 T2 125 100 90 100 80 100 100 T3 125 60 30 60 90 100 100 T4 125 80 90 90 80 80 100 T5 125 70 70 80 90 100 100 T6 125 80 80 80 80 90 90 T7 125 100 90 90 90 70 90 T8 125 100 100 100 100 100 100 T9 125 80 60 70 80 100 100 T10 125 70 70 80 80 50 80 T11 125 40 20 30 70 80 70 T12 125 70 50 10 70 70 70 T13 125 80 90 90 100 50 100 T14 125 80 80 80 100 90 100 T15 125 50 40 40 50 80 80 T16 125 40 20 50 0 0 30 T17 125 100 100 90 100 100 100 T18 125 100 100 80 100 100 100 T19 125 100 100 90 100 90 100 T21 125 90 70 70 60 30 100 T27 125 100 90 80 100 100 100 T34 125 40 30 30 80 80 80 T37 125 50 20 20 70 50 80 T39 125 10 20 0 60 70 70 T40 125 40 30 30 70 70 70 T41 125 40 0 0 80 80 80 T42 125 0 0 10 0 20 60 T43 125 10 0 0 40 20 60 T44 125 80 50 20 80 80 90 T46 125 0 0 0 60 0 80 T47 125 100 90 90 70 60 100 T48 125 80 70 70 90 100 100 T49 125 80 80 70 50 70 80 T52 125 60 70 70 80 80 100 T56 125 100 50 80 60 70 100 T57 125 70 70 40 70 70 80 T58 125 0 10 0 30 40 30 T59 125 50 40 0 70 80 80 T60 125 10 0 0 40 50 0 T62 125 60 0 20 70 70 80 T64 125 10 0 0 30 60 50 T65 125 90 90 80 100 100 100 T66 125 80 80 50 80 90 80 T70 125 90 70 70 70 70 80 T71 125 50 10 20 50 70 60 T85 125 90 20 70 70 20 100 T89 125 80 80 80 90 90 100 T90 125 90 80 60 60 80 80 T91 125 90 90 50 100 100 100 T92 125 100 100 50 100 100 100 T93 125 60 80 60 100 100 100 T97 125 90 90 80 100 100 100 T98 125 70 20 40 70 60 80 T99 125 80 30 10 70 60 100 T106 125 90 80 80 90 80 100 T107 125 100 90 90 100 100 100 T125 125 80 70 70 80 80 90 T128 125 80 90 80 100 100 100 T129 125 80 80 70 100 80 100 T134 125 20 20 20 50 20 70 T143 125 40 60 30 40 60 70 T146 125 80 80 90 70 70 100 T147 125 90 90 40 70 100 90 T149 125 80 90 70 70 80 100 T150 125 60 60 40 90 30 100 T151 125 80 80 30 10 70 80 T153 125 50 80 50 20 30 70 T154 125 90 60 60 70 70 100 T155 125 90 70 60 100 100 100 T156 125 90 80 70 100 70 100 T157 125 60 60 40 60 60 100 T158 125 90 90 80 100 100 100 T159 125 90 70 40 100 100 100 T160 125 90 90 70 100 100 100 T162 125 90 90 70 100 100 100 T163 125 80 80 80 90 70 100 T165 125 80 30 80 90 70 100 T167 125 80 50 50 70 70 100 T169 125 90 10 30 60 40 80 T170 125 80 70 80 40 40 100 T171 125 70 60 20 90 80 100 T173 125 100 90 90 90 70 100 T174 125 70 70 40 50 70 80 T177 125 80 70 30 20 30 80 T178 125 100 90 90 100 100 100 T179 125 80 80 80 10 50 70 T180 125 90 70 70 100 90 100 T181 125 90 90 80 100 80 100 T182 125 100 90 80 100 100 100 T184 125 10 0 10 50 20 100 T185 125 90 80 80 100 100 100 T187 125 70 10 40 60 60 70 T188 125 80 70 30 70 100 100 T193 125 60 40 30 30 60 60 T194 125 30 0 20 0 70 80 T199 125 100 100 60 80 100 100 T200 125 70 80 80 100 100 100 T203 125 20 10 10 0 50 50 T208 125 70 70 80 70 50 80 P3 125 100 90 100 80 70 100 P4 125 100 90 100 90 80 100 P5 125 100 90 100 80 60 100 P6 125 100 90 100 80 80 100 P9 125 100 90 100 80 80 90 P10 125 100 90 100 80 80 100 P14 125 90 90 90 100 100 100 P15 125 100 90 90 80 80 100 P16 125 100 90 100 100 100 100 P17 125 100 90 100 100 100 100 P18 125 90 50 80 70 70 100 P19 125 100 100 100 100 100 100 P20 125 100 100 100 90 80 100 P21 125 90 100 100 100 80 100 P22 125 100 100 100 100 100 100 P23 125 100 90 90 80 70 100 P24 125 100 100 100 100 70 100 P25 125 100 90 100 80 80 100 P26 125 100 100 90 100 100 100 P24 125 80 60 70 90 100 90 P28 125 80 80 70 80 80 100 P30 125 80 NC 70 80 90 100 P33 125 80 70 80 70 70 90 P36 125 60 70 60 80 80 90 P37 125 90 80 90 100 90 100

Test Example 2

Test compounds were applied post-emergence at 60 g ai/ha, alone and in combination with cloquintocet-mexyl at 60 g ai/ha; the adjuvant Adigor (0.5%) was included for every treatment. The application volume was 2001/ha. Target plants were 2-3 leaf seedlings of winter wheat ‘Hereward’ and winter barley ‘Antoniya’ grown in a greenhouse under ambient conditions. Assessments were made at 14-21 days after application.

Cloquintocet- Rate mexyl Crop Injury (%) Compound (g/ha) (g/ha) Wheat Barley T1 60 0 85 99 60 60 18 73 T3 60 0 28 5 60 60 0 5 1:1 mixture of 60 0 63 85 T106:T107 60 60 23 45

Test Example 3

The test compound T1 was applied at 100 and 200 g ai/ha, alone and in combination with a range of safeners as 1:1 mixtures (for example at 100 g+100 g; 200 g+200 g) to the test plants—wheat and maize—at the 2-3 leaf stage. A 4-way safener mixture (cloquintocet-mexyl, benoxacor, fluxofenim and compound A*) was also applied with the test compound so that each safener was used a 1:1 ratio (for example at 100+100+100+100+100 g ai/ha). Assessments were made at 14-21 days after application.

Wheat Injury (%) Maize Injury (%) Test Sample 100 g/ha 200 g/ha 100 g/ha 200 g/ha T1 alone 83 92 90 100 T1 + benoxacor at 1:1 80 85 90 75 ratio T1 + cloquintocet-mexyl 5 10 93 95 at 1:1 ratio T1 + isoxadifen at 1:1 65 73 65 75 ratio T1 + cyprosulfamide 68 85 23 28 at 1:1 ratio T1 + compound A* at 73 88 30 35 1:1 ratio T1 + fluxofenim at 1:1 75 90 85 88 ratio T1 + mefenpyr-diethyl 23 45 100 100 at 1:1 ratio T1 + dichlormid at 1:1 73 73 80 100 ratio T1 + 4-way mix at 0 20 30 50 1:1:1:1 ratio *Compound A is N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide. 

1. A compound of formula I

wherein G is hydrogen or an alkali metal, alkaline earth metal, sulfonium, ammonium or a latentiating group, R¹ is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, ethynyl, halogen, C₁-C₂alkoxy or C₁-C₂haloalkoxy, R², R³ and R⁴ are independently of each other hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, ethynyl, halogen, C₁-C₂alkoxy or C₁-C₂ haloalkoxy, R⁵ and R¹² are independently of each other hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkyoxy, C₁-C₃alkylthio, halogen or C₁-C₆alkoxycarbonyl, or R⁵ and R¹² join together to form a 3-7 membered carbocyclic ring, optionally containing an oxygen or sulfur atom, and R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are independently of each other hydrogen or a substituent, or R⁷ and R⁸, or R⁹ and R¹⁰, together with the carbon atoms to which they are attached form a keto, an optionally substituted alkenyl or optionally substituted imino unit, or any two of R⁷, R⁸, R⁹ and R¹⁰ together form a 3-8 membered carbocyclic ring optionally containing a heteroatom selected from O, S or N and optionally substituted, or R⁷ and R¹⁰ together form a bond.
 2. A compound according to claim 1, wherein R⁶ and R¹¹ are independently of each other hydrogen, halogen, formyl, cyano or nitro or R⁶ and R¹¹ are independently of each other C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₆alkoxy, C₃-C₇ cycloalkyl, C₃-C₇ cycloalkenyl, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, or R⁶ and R¹¹ are independently of each other a group COR¹³, CO₂R¹⁴ or CONR¹⁵R¹⁶, CR¹⁷═NOR¹⁸, CR¹⁹═NNR²⁰R²¹, NHR²², NR²²R²³ or OR²⁴, wherein R¹³ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, R¹⁴ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, phenyl, heteroaryl or is 3-7 membered heterocyclyl, where all these substituents are optionally substituted, R¹⁵ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, R¹⁶ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, C₁-C₆alkylsulfonyl, phenylsulfonyl, heteroarylsulfonyl, amino, C₁-C₆alkylamino, diC₁-C₆alkylamino, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, or R¹⁵ and R¹⁶ may be joined to form an optionally substituted 3-7 membered ring, optionally containing an oxygen, sulfur or nitrogen atom, R¹⁷ and R¹⁹ are independently of each other hydrogen, C₁-C₃alkyl or C₃-C₆cycloalkyl, R¹⁸, R²⁰ and R²¹ are independently of each other hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, aminocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, phenyl or heteroaryl, where all these substituents are optionally substituted, R²² is C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, C₁-C₆alkylsulfonyl, phenylcarbonyl, phenoxycarbonyl, phenylaminocarbonyl, phenylthiocarbonyl, phenylsulfonyl, heteroarylcarbonyl, heteroaryloxycarbonyl, heteroarylaminocarbonyl, heteroarylthiocarbonyl or heteroarylsulfonyl, where all these substituents are optionally substituted, R²³ is C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, C₁-C₆alkylsulfonyl, phenyl or heteroaryl, where all these substituents are optionally substituted, or R²² and R²³ may be joined to form an optionally substituted 3-7 membered ring, optionally containing an oxygen, sulfur or nitrogen atom, where all these substituents are optionally substituted, and R²⁴ is C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, aminocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, tri(C₁-C₆alkyl)silyl, phenyl or heteroaryl, where all these substituents are optionally substituted.
 3. A compound according to claim 1, wherein R⁷, R⁸, R⁹ and R¹⁰ are independently of each other hydrogen, halogen, hydroxyl, formyl, amino, cyano or nitro, or R⁷, R⁸, R⁹ and R¹⁰ are independently of each other C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆alkoxyC₁-C₆alkyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆alkylthioC₁-C₆alkyl, C₁-C₆alkylsulfinylC₁-C₆alkyl, C₁-C₆alkylsulfonylC₁-C₆alkyl, C₃-C₇ cycloalkyl, C₄-C₇cycloalkenyl, tri(C₁-C₆alkyl)silyl, aryl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, or R⁷, R⁸, R⁹ and R¹⁰ are independently of each other a group COR¹³, CO₂R¹⁴ or CONR¹⁵R¹⁶, CR¹⁷═NOR¹⁸, CR¹⁹═NNR²⁰R²¹, NR²²R²³ or OR²⁴, wherein R¹³ is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, R¹⁴ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, phenyl, heteroaryl or is 3-7 membered heterocyclyl, where all these substituents are optionally substituted, R¹⁵ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, R¹⁶ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₇ cycloalkyl, C₅-C₇cycloalkenyl, C₁-C₆alkylsulfonyl, amino, C₁-C₆alkylamino, diC₁-C₆alkylamino, phenyl, heteroaryl or a 3-7 membered heterocyclyl, where all these substituents are optionally substituted, or R¹⁵ and R¹⁶ may be joined to form an optionally substituted 3-7 membered ring, optionally containing an oxygen, sulfur or nitrogen atom, R¹⁷ and R¹⁹ are independently of each other hydrogen, C₁-C₃alkyl or C₃-C₆cycloalkyl, R¹⁸, R²⁰ and R²¹ are independently of each other hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, phenyl or heteroaryl, where all these substituents are optionally substituted, R²² and R²³ are independently of each other C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, C₁-C₆alkylsulfonyl, phenyl or heteroaryl or R²² and R²³ may be joined to form an optionally substituted 3-7 membered ring, optionally containing an oxygen, sulfur or nitrogen atom, where all these substituents are optionally substituted, and R²⁴ is C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₃-C₇ cycloalkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylthiocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, C₁-C₆alkylsulfonyl, tri(C₁-C₆alkyl)silyl, phenyl or heteroaryl, where all these substituents are optionally substituted.
 4. A compound according to claim 1, wherein — R⁷ and R⁸, or R⁹ and R¹⁰, together form a unit ═O, or form a unit ═CR²⁵R²⁶, or form a unit ═NR²⁷, or any two of R⁷, R⁸, R⁹ and R¹⁰ form a 3-8 membered ring, optionally containing a heteroatom selected from O, S or N and optionally substituted by C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃haloalkyl, halogen, phenyl, phenyl substituted by C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl, aminocarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, halogen, cyano or by nitro, heteroaryl or heteroaryl substituted by C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylcarbonyl, halogen, cyano or by nitro, wherein R²⁵ and R²⁶ are independently of each other hydrogen, halogen, cyano or nitro, or R²⁵ and R²⁶ are independently of each other C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkylamino, diC₁-C₆alkylamino, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylaminocarbonyl, diC₁-C₆alkylaminocarbonyl, N-phenyl-N—C₁-C₆alkylaminocarbonyl, N-phenylC₁-C₆alkyl-N—C₁-C₆alkylaminocarbonyl, N-heteroaryl-N—C₁-C₆alkylaminocarbonyl, N-heteroarylC₁-C₆alkyl-N—C₁-C₆alkylaminocarbonyl, phenyl, heteroaryl, C₃-C₆cycloalkyl or 3-7 membered heterocyclyl, where all these substituents are optionally substituted, or R²⁵ and R²⁶ may be joined together to form a 5-8 membered ring optionally containing a heteroatom selected from O, S or N and optionally substituted by C₁-C₂alkyl or C₁-C₂alkoxy, R²⁷ is nitro or cyano, or R²⁷ is C₁-C₆alkylamino, diC₁-C₆alkylamino, C₁-C₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, phenoxy, phenylamino, N-phenyl-N—C₁-C₆alkylamino, N-phenylC₁-C₆alkyl-N—C₁-C₆alkylamino heteroaryloxy, heteroarylamino, N-heteroaryl-N—C₁-C₆alkylamino or N-heteroarylC₁-C₆alkyl-N—C₁-C₆alkylamino, where all these substituents are optionally substituted.
 5. A compound according to claim 1, wherein R¹, R² and R⁴ are methyl and R³ is hydrogen.
 6. A compound according to claim 1, wherein R¹, R² and R⁴ are methyl and R³ is hydrogen, and R⁷, R⁸, R⁹ and R¹⁰ are independently of each other hydrogen, cyano, C₁-C₆alkyl, C₂-C₆alkenyl, C₁-C₆alkoxy, C₁-C₆alkoxyC₁-C₆alkyl, 3-7 membered heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl.
 7. A compound according to claim 1, wherein R⁵ and R¹² are independently of each other hydrogen or C₁-C₃alkyl.
 8. A compound according to claim 1, wherein R¹ is methyl, ethyl, vinyl, ethynyl, cyclopropyl, difluoromethoxy, trifluoromethoxy or C₁-C₂ alkoxy and R², R³ and R⁴ are independently of each other hydrogen, methyl, ethyl, vinyl or ethynyl.
 9. A process for the preparation of a compound of formula (AH)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁸, R⁹, R¹¹ and R¹² are as defined in claim 1, which comprises reacting a compound of formula (H)

with a compound of formula (AI)

in the presence or absence of a catalyst and in the presence or absence of a solvent.
 10. A compound of formula (AI)

wherein R¹, R², R³, R⁴, R⁵ and R¹² are as defined in claim 1, where the compounds of the formulae

are excluded.
 11. A herbicidal composition, which, in addition to comprising formulation adjuvants, comprises a herbicidally effective amount of a compound of formula I.
 12. A herbicidal composition according to claim 11, which, in addition to comprising formulation adjuvants, comprises a herbicidally effective amount of a compound of formula I and a further herbicide.
 13. A herbicidal composition according to claim 11, which, in addition to comprising formulation adjuvants, comprises a herbicidally effective amount of a compound of formula I, a further herbicide and a safener.
 14. A method of controlling grasses and weeds in crops of useful plants, which comprises applying a herbicidally effective amount of a compound of formula I, or of a composition comprising such a compound, to the plants or to the locus thereof. 